CN116444357A - 1, 5-dicarbonyl compound and synthesis method and application thereof - Google Patents

1, 5-dicarbonyl compound and synthesis method and application thereof Download PDF

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CN116444357A
CN116444357A CN202310372682.8A CN202310372682A CN116444357A CN 116444357 A CN116444357 A CN 116444357A CN 202310372682 A CN202310372682 A CN 202310372682A CN 116444357 A CN116444357 A CN 116444357A
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phenyl
dicarbonyl compound
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catalyst
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罗三中
张文昭
张龙
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Tsinghua University
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Tsinghua University
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Abstract

The application provides a 1, 5-dicarbonyl compound, a synthesis method and application thereof, wherein the synthesis method of the 1, 5-dicarbonyl compound comprises the steps of mixing the 1, 3-dicarbonyl compound and an olefin compound in an organic solvent under the protection of inert gas, and reacting under the condition of stirring and light source irradiation under the action of a zirconium-containing catalyst to generate the 1, 5-dicarbonyl compound. The synthesis method of the 1, 5-dicarbonyl compound takes the 1, 3-dicarbonyl compound and the olefin compound as raw materials under the protection of inert gas, utilizes the zirconium-containing catalyst to synthesize the chiral or achiral 1, 5-dicarbonyl compound under the conditions of stirring and light source irradiation, has the characteristics of mild, high efficiency and environment friendliness, and can realize the catalytic asymmetric process. The method can react under the protection of inert gas by direct illumination, does not need heating, does not need additives, generates non-toxic byproducts, and has the atomic economy of 100 percent.

Description

1, 5-dicarbonyl compound and synthesis method and application thereof
Technical Field
The application relates to the technical field of synthesis of dicarbonyl compounds, in particular to a 1, 5-dicarbonyl compound and a synthesis method and application thereof.
Background
Zirconium is a widely existing metal in nature, has abundant reserves and low price, and various complexes containing the metal can be widely used as Lewis acid in organic compound conversion and high polymer compound synthesis. However, research on the promotion of the zirconium catalytic reaction by the visible light is relatively deficient, and further development is needed.
The process of 1, 3-dicarbonyl compound and alkene undergo [2+2] cycloaddition under illumination condition, and then the 1, 5-dicarbonyl compound is obtained through inverse Aldol reaction, which was found by Paul de Mayo professor in 1962, and is called de Mayo reaction. The reaction has been successfully applied to the total synthesis of various natural products and pharmaceutically active molecules, and has high practical value. The synthesis of the 1, 5-dicarbonyl compound can be realized through de Mayo reaction, the compound is widely applied to the fields of medical treatment, materials, scientific research and the like, and part of the compound has biological activities of resisting tumor, reducing blood fat and cholesterol, resisting bacteria and the like. Meanwhile, the compound is an important intermediate in synthetic chemistry and chemical industry, and can be used for synthesizing organic matters such as heterocyclic compounds in organic transformation. Therefore, a method for efficiently synthesizing the compound may have a high practical value.
At present, few reports on the visible light promotion of organic conversion reaction involving zirconium complexes are reported, and partial reports on the visible light responsiveness of the zirconium complexes are focused in MOF materials and are not taken as catalytic active centers to participate in the reaction. The 1, 5-dicarbonyl compound is mainly obtained by Michael addition process, specifically by 1, 4-nucleophilic addition of a nucleophilic reagent containing carbonyl group and alpha, beta-unsaturated carbonyl compound.
However, when the Michael addition process is used for synthesizing the 1, 5-dicarbonyl compound, the raw materials have higher toxicity, the reaction conditions are more severe, the synthesis efficiency of the achiral 1, 5-dicarbonyl compound is low, and the chiral 1, 5-dicarbonyl compound is difficult to obtain. For de Mayo reaction, the reaction usually uses ultraviolet light source with high energy, which is not friendly to environment and limits the application range, while the process of promoting visible light is not successfully realized until recently, and the efficiency is still provided with further improved space
Disclosure of Invention
In view of this, an object of the present application is to provide a method for synthesizing a 1, 5-dicarbonyl compound, which uses a 1, 3-dicarbonyl compound and an olefin compound as raw materials under the protection of inert gas, and synthesizes a chiral or achiral 1, 5-dicarbonyl compound under the conditions of stirring and light source irradiation by using a zirconium-containing catalyst, and has the characteristics of mild, high efficiency, environmental protection, and capability of realizing a catalytic asymmetric process. The method can react under the protection of inert gas by direct illumination, does not need heating or additives, generates no toxic byproducts, has the atomic economy of 100 percent, and can recycle raw materials.
It is another object of the present application to provide a 1, 5-dicarbonyl compound.
It is a further object of the present application to provide the use of a 1, 5-dicarbonyl compound.
To achieve the above object, an embodiment of the first aspect of the present application provides a method for synthesizing a 1, 5-dicarbonyl compound, comprising:
under the protection of inert gas, mixing the 1, 3-dicarbonyl compound and the olefin compound in an organic solvent, and reacting under the conditions of stirring and light source irradiation under the action of a zirconium-containing catalyst to generate the 1, 5-dicarbonyl compound.
In some embodiments, the inert atmosphere includes, but is not limited to, one or more of nitrogen, helium, argon, and the like.
It should be noted that the synthesis method of the 1, 5-dicarbonyl compound in the embodiment of the present application may be used for synthesis of chiral 1, 5-dicarbonyl compounds, and may also be used for synthesis of achiral 1, 5-dicarbonyl compounds, and the two main differences are that the types of zirconium-containing catalysts are different.
Specifically, when used for the synthesis of chiral 1, 5-dicarbonyl compounds:
in some embodiments, the zirconium-containing catalyst comprises a first catalyst and a second catalyst, the first catalyst comprising, but not limited to, zrCl 4 、Zr(OTf 3 ) 4 、ZrBr 4 、Zr(O n Pr) 4 、ZrF 4 、ZrOCl 2 、Zr(OH) 4 、Zr(OAc) 4 、Zr[(PhO) 2 POO] 4 、Zr[( p OMePhO) 2 POO] 4 、Zr[( p ClPhO) 2 POO] 4 、Zr[( p BrPhO) 2 POO] 4 One or more of the following; the second catalyst is chiral phosphoric acid. In some embodimentsIn one example, the chiral phosphoric acid has the structure of formula (I):
wherein R is 1 、R 2 Each independently selected from phenyl,One of them.
At this time, in some embodiments, the 1, 3-dicarbonyl compound has the structure of formula (III), wherein R 5 Is phenyl or phenyl containing substituent, R 6 Is one of phenyl, phenyl containing substituent and C1-4 alkyl.
In some embodiments, the olefin compound has the structure of formula (IV), wherein R 7 Is phenyl or phenyl containing substituent.
In some embodiments, the 1, 5-dicarbonyl compound is a chiral 1, 5-dicarbonyl compound having the structure of formula (V),
in the formula (V), R 8 Is phenyl or phenyl containing substituent, R 9 Is one of phenyl, phenyl containing substituent and C1-4 alkyl, R 10 Is phenyl or phenyl containing substituent.
The principle of the synthetic reaction of chiral 1, 5-dicarbonyl compounds can be expressed as formula (1):
r is as follows 8 And R is R 5 Identical, R 9 And R is R 6 Identical, R 10 And R is R 7 The same applies. Wherein when R is 5 And R is 8 When phenyl having substituents, substituents include, but are not limited to, alkoxy, alkyl, haloalkyl, halogen, and the like, including, but not limited to, C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, and the like. When R is 9 And R is 6 When phenyl having substituents, substituents include, but are not limited to, alkoxy, alkyl, haloalkyl, halogen, and the like, including, but not limited to, C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, and the like. When R is 10 And R is 7 When phenyl having substituents, substituents include, but are not limited to, alkoxy, alkyl, haloalkyl, halogen, and the like, including, but not limited to, C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, and the like.
In some embodiments, the method of synthesizing a chiral 1, 5-dicarbonyl compound comprises the steps of:
before the reaction of the 1, 3-dicarbonyl compound and the olefin compound, the 1, 3-dicarbonyl compound is reacted with a first catalyst and a second catalyst to generate an intermediate shown in a formula (II), and then the intermediate shown in the formula (II) and the olefin compound are mixed in an organic solvent and react under the conditions of stirring and light source irradiation to generate chiral 1, 5-dicarbonyl compound;
in the formula (II), R 3 Is phenyl or phenyl containing substituent, R 4 Is phenyl or one of phenyl and C1-4 alkyl containing substituent. In the synthesis process of chiral 1, 5-dicarbonyl compound, R 3 、R 5 、R 8 All three are the same, R 4 、R 6 And R is R 9 All three are identical, and when each is phenyl having a substituent, the substituents are specifically selected as in the previous (R 8 And R is R 5 Identical, R 9 And R is R 6 The same situation), and will not be described in detail herein.
In other embodiments, the method of synthesizing a chiral 1, 5-dicarbonyl compound further comprises: and (2) before the reaction of the 1, 3-dicarbonyl compound and the olefin compound, reacting part of the 1, 3-dicarbonyl compound with the first catalyst and the second catalyst to generate an intermediate shown in the formula (II), mixing the intermediate shown in the formula (II), the other part of the 1, 3-dicarbonyl compound and the olefin compound in an inert atmosphere in an organic solvent, and reacting under stirring and light source irradiation conditions to generate the chiral 1, 5-dicarbonyl compound. Preferably, the molar amount of the 1, 3-dicarbonyl compound reacted with the first catalyst and the second catalyst to form the intermediate of the above formula (II) is m mol, the molar amount of the 1, 3-dicarbonyl compound mixed with the intermediate of the formula (II) and the olefin compound in an inert atmosphere in an organic solvent is n mol, and n=1 (1-20), including but not limited to 1: 20. 1:10, 1:5, 1:2, or 1:1, etc.
It is understood that in the synthesis of chiral 1, 5-dicarbonyl compounds of the present application, the intermediate of formula (II) may be obtained by previously mixing the first and second catalysts (chiral phosphoric acid) and the 1, 3-dicarbonyl compound of formula (III) and then separating. The intermediate may be irradiated with an olefin compound represented by the formula (IV) under stirring with a light source to obtain the target compound represented by the formula (v), or may be used as a catalyst for the reaction in place of the first catalyst and the second catalyst (chiral phosphoric acid) to catalyze the same reaction between the 1, 3-dicarbonyl compound represented by the formula (III) and the olefin compound represented by the formula (IV). Wherein the first catalyst is ZrCl 4 The second catalyst isFormula (III) is->Formula (IV) isThe (V) is/>The intermediate formula (II) is->By way of example, one possible reaction principle involved is shown in formulas (1-1) - (1-5):
wherein [ formula (II)] * The formula (II) and the formula (IX) in the excited state are respectively:
in some embodiments, the organic solvent is one or more of chloroform, dichloromethane, 1, 2-dichloroethane. Preferably, the organic solvent is chloroform.
In some embodiments, the light source is visible light. Preferably, the light source is a 10W 400nm LED.
In some embodiments, the first catalyst is added in an amount of 2.5 to 7.5mol%, including but not limited to 2.5mol%, 3mol%, 3.5mol%, 4mol%, 4.5mol%, 5mol%, 5.5mol%, 6mol%, 6.5mol%, 7mol%, or 7.5mol%, etc.
In some embodiments, the second catalyst is added in an amount of 10-20mol%, including but not limited to 10mol%, 11mol%, 12mol%, 13mol%, 14mol%, 15mol%, 16mol%, 17mol%, 18mol%, 19mol%, 20mol%, etc.
As a possible example, in the synthesis process of chiral 1, 5-dicarbonyl compound, the first catalyst is ZrCl 4 The second catalyst isThe amount of the first catalyst added was 5mol%, and the amount of the second catalyst added was 15mol%.
In the present application, when the synthesis method of the 1, 5-dicarbonyl compound is used for the synthesis of the achiral 1, 5-dicarbonyl compound:
in some embodiments, the zirconium-containing catalyst includes, but is not limited to, zrCl 4 、Zr[(PhO) 2 POO] 4 、Zr[( p OMePhO) 2 POO] 4 、Zr[( p ClPhO) 2 POO] 4 、Zr[( p BrPhO) 2 POO] 4 、Zr(O n Pr) 4 、Zr(HPO 4 ) 2 、ZrOCl 2 、Zr(OH) 4 、Zr(OAc) 4 、ZrH 2 、Cp 2 ZrCl 2 、CpZrCl 3 、( n Bu)Cp 2 CrCl 2 Indene ZrCl 2 (CAS: 100080-82-8), indene ZrCl 3 (CAS: 82161-76-0), indene 2 ZrCl 2 (CAS: 12148-49-1). Biindene ZrCl 2 (CAS: 100080-82-8), indene ZrCl 3 (CAS: 82161-76-0), indene 2 ZrCl 2 (CAS: 12148-49-1) the structural formulae are as follows:
biindene ZrCl 2 ：Indene ZrCl 3 ：/>Indene (indene) 2 ZrCl 2 ：/>
In other embodiments, the zirconium-containing catalyst comprises a first catalyst and a second catalyst, the first catalyst being ZrCl 4 The method comprises the steps of carrying out a first treatment on the surface of the The second catalyst is achiral phosphoric acid. As a non-limiting example, the molar ratio of the first catalyst to the second catalyst during synthesis of the achiral 1, 5-dicarbonyl compound is 2-1:3-0.01, including but not limited to 1:1, 1:2, 1:3, 2:1, or 1:0.01, and the like.
In some embodiments, achiral phosphoric acid as the second catalyst includes, but is not limited to (PhO) 2 POOH、( p OMePhO) 2 POOH、( p ClPhO) 2 POOH、( p BrPhO) 2 One or more of POOH.
In some embodiments, the 1, 3-dicarbonyl compound has the structure of formula (VI),
in the formula (VI), R is 11 Is phenyl or phenyl containing substituent, R 12 Is one of phenyl, phenyl containing substituent, C1-3 alkyl and amino with substituent.
In some embodiments, the olefin compound has the structure of formula (VII),
in the formula (VII), R 13 Is one of hydrogen, phenyl, C1-8 aryl containing substituent, C1-18 alkyl and acetoxy, R 14 And R is 15 Each independently represents one of hydrogen, phenyl, C1-8 aryl containing substituent, C1-18 alkyl and acetoxy.
In some embodiments, the 1, 5-dicarbonyl compound is an achiral 1, 5-dicarbonyl compound having the structure of formula (VIII),
in the formula (VIII), R 16 Is phenyl or phenyl containing substituent, R 17 Is one of phenyl, phenyl containing substituent, C1-3 alkyl and amino with substituent, R 18 Is one of phenyl, C1-8 aryl containing substituent, C1-18 alkyl and acetoxy, R 19 And R is 20 Each independently represents one of phenyl, C1-8 aryl containing substituent, C1-18 alkyl and acetoxy.
In the present application, the principle of the synthesis reaction of achiral 1, 5-dicarbonyl compounds can be expressed as formula (2):
wherein R is 11 And R is R 16 Identical, R 12 At R 17 Identical, R 13 And R is R 18 Identical, R 14 At R 19 Identical, R 15 And R is R 20 The same applies. Wherein when R is 11 And R is 16 When phenyl is substituted, the substituents include, but are not limited to, alkoxy, alkyl, halo, haloalkyl, cyano, and the like, including, but not limited to, C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, and the like. When R is 12 And R is 17 When phenyl having substituents, substituents include, but are not limited to, cyano, haloalkyl, halogen, alkyl, alkoxy, and the like, including, but not limited to, C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, and the like; when R is 12 And R is 17 When an amino group having a substituent, the substituent includes, but is not limited to, phenyl, benzyl, phenyl, etc., having a first substituent including, but not limited to, C1-4 haloalkyl, C1-4 alkyl, etc. When R is 13 And R is 18 In the case of phenyl groups containing substituents, substituents include, but are not limited toCyano, haloalkyl, halogen, alkyl, alkoxy, and the like, including but not limited to C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, and the like. When R is 14 And R is 19 When phenyl is substituted, the substituents include, but are not limited to, cyano, haloalkyl, halogen, alkyl, alkoxy, and the like, including, but not limited to, C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, and the like. When R is 15 And R is 20 When phenyl is substituted, the substituents include, but are not limited to, cyano, haloalkyl, halogen, alkyl, alkoxy, and the like, including, but not limited to, C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, and the like.
In some embodiments, the organic solvent is one or more of dichloromethane, chloroform, ethyl acetate, ethanol, acetonitrile, isopropanol, 1, 2-dichloroethane. Preferably, the organic solvent is Dichloromethane (DCM), preferably at a concentration of 0.1M, during the synthesis of the achiral 1, 5-dicarbonyl compound.
In some embodiments, the light source is 10W 400-440nm visible light. Preferably, the light source is a 10W 440nm LED; when R in formula (VI) 12 A10W 400nm LED was used for C1-3 alkyl or NHBn.
In some embodiments, the zirconium-containing catalyst is added in an amount of 2-10mol% during the synthesis of the achiral 1, 5-dicarbonyl compound, including but not limited to 2mol%, 3mol%, 4mol%, 5mol%, 6mol%, 7mol%, 8mol%, 9mol%, 10mol%, etc.
As a possible example, the zirconium-containing catalyst during the synthesis of the achiral 1, 5-dicarbonyl compound is biindene ZrCl2 (CAS: 100080-82-8) added in an amount of 2mol%. When R in formula (VI) 12 When the catalyst is an amino group having a substituent, the amount of the zirconium-containing catalyst added is 10mol%.
In some embodiments, the molar amount of 1, 3-dicarbonyl compound is a mole, the molar amount of olefin compound is b mole, and a and b satisfy the following relationship, regardless of the chiral 1, 5-dicarbonyl compound synthesis process or the achiral 1, 5-dicarbonyl compound synthesis process: a-1/b-1=1/2, and a and b are both greater than 0. As non-limiting examples, the values of a/b include, but are not limited to, 1/2, 1/3, 2, etc. Preferably, the value of a/b is 1/2.
In order to achieve the above object, a second aspect of the present application provides a 1, 5-dicarbonyl compound represented by the general formula (V) or a pharmaceutically acceptable salt thereof, synthesized by the synthesis method of the embodiment of the present application,
In the formula (V), R 8 Is phenyl or phenyl containing substituent, R 9 Is one of phenyl, phenyl containing substituent and C1-4 alkyl, R 10 Is phenyl or phenyl containing substituent.
To achieve the above object, an embodiment of the third aspect of the present application relates to the use of the 1, 5-dicarbonyl compound represented by general formula (V) or a pharmaceutically acceptable salt thereof according to the embodiment of the present application or the 1, 5-dicarbonyl compound synthesized by the synthesis method according to the embodiment of the present application in the biomedical field or the heterocyclic compound synthesis field.
The synthesis method of the 1, 5-dicarbonyl compound has the following beneficial effects:
under the protection of inert gas, the 1, 3-dicarbonyl compound and the olefin compound are used as raw materials, the zirconium-containing catalyst is utilized to synthesize the chiral or achiral 1, 5-dicarbonyl compound under the conditions of stirring and light source irradiation, and the method has the characteristics of mild, high efficiency, environmental protection and capability of realizing the catalytic asymmetric process. The method can react under the protection of inert gas by direct illumination, does not need heating or additives, generates no toxic byproducts, has the atomic economy of 100 percent, and can recycle raw materials.
The following explanation of the terms of the present application is provided for the specific terms, if the meaning in the present application is not consistent with the meaning commonly understood by those skilled in the art, the meaning in the present application is taken into consideration; if not defined in the present application, it has a meaning commonly understood by those skilled in the art. Unless stated to the contrary, the terms used in this application have the following meanings:
In this application, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a particular substituent. Unless otherwise indicated, a substituent may be substituted at each substitutable position of a given structure. When more than one position in a given structure can be substituted with one or more substituents selected from a particular group, then the substituents may be the same or different at each position. "substituted phenyl" means a phenyl group which is mono-or polysubstituted.
In the present application, the term "C1-xx alkyl" refers to a straight or branched alkyl group having 1-xx (xx refers to the upper limit number of carbon atoms, for example when xx is 10, representing the upper limit of the number of carbon atoms of 10) carbon atoms; examples thereof include methyl, ethyl, propyl, isopropyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-ethylpropyl, butyl, tert-butyl, pentyl, hexyl, and the like, and it is to be construed that alkyl groups having various morphological structures including C1, C2, C3, C4, C5, C6, C7, C8, CX (e.g., C10) are not limited to the examples listed above.
As used herein, the term "aryl" refers to an aromatic carbocyclic group having a single ring (e.g., phenyl), multiple rings (e.g., naphthyl), or fused rings in which at least one ring is aromatic (e.g., 1,2,3, 4-tetrahydronaphthyl). For example an aryl group containing 5 to 20 (e.g. 5 to 15 or 5 to 10) carbon atoms. Specific examples include, but are not limited to, phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, acenaphthylenyl, and the like.
In the present application, the term "acetoxy" is a functional group having the structure-O-C (=o) -CH 3.
In the present application, the term "alkoxy" is generally denoted by RO-and means a radical composed of an alkyl group and an oxygen atom, for example: methoxy (CH) 3 O-), ethoxy (C) 2 H 5 O-), propoxy (C) 3 H 7 O-) and the like.
In the present application, the term "haloalkyl" refers to a functional group formed by partial or complete substitution of hydrogen atoms in an alkyl group with halogen atoms.
In this application, the term "halogen" may be fluorine, chlorine, bromine or iodine.
As used herein, the term "benzyl" refers to a group (C) formed by removing a hydrogen atom from the methyl carbon in a toluene molecule 6 H 5 CH 2 -)。
In this application, the term "cyano" refers to a group (-CN) in which a carbon atom and a nitrogen atom are linked by a triple bond.
The term "pharmaceutically acceptable" as used herein generally refers to being pharmaceutically or medically useful or, although not directly applicable to the manufacture of pharmaceutical or medical product intermediates, being available for use in the manufacture of pharmaceutical or medical products and removed by suitable means prior to final use in the pharmaceutical or medical. For example, pharmaceutically acceptable salts include not only pharmaceutically acceptable salts that are clinically useful, but also salts that are not directly clinically useful, but which are useful in the preparation of the compounds of the present application and which are removed during subsequent processing. The term "pharmaceutically acceptable salts" as used herein includes conventional salts with pharmaceutically acceptable inorganic or organic acids or bases and salts of quaternary amines with acids. Examples of suitable acid salts include, but are not limited to, hydrochloride, hydrobromide, sulfate, phosphate, nitrate, perchlorate, fumarate, acetate, propionate, pyruvate, succinate, glycolate, formate, lactate, maleate, tartrate, citrate, pamoate, malonate, glutarate, hydroxymaleate, phenylacetate, glutamate, benzoate, salicylate, fumarate, tosylate, mesylate, naphthalene-2-sulfonate, benzenesulfonate, hydroxynaphthoate, hydroiodide, malate, stearate, tannate, and the like. Other salts, such as oxalates, although not pharmaceutically acceptable per se, may be used to prepare salts useful as intermediates to obtain the compounds of the present application and pharmaceutically acceptable salts thereof. More specific examples of suitable base salts include sodium, lithium, potassium, magnesium, aluminum, calcium, zinc, ammonium, triethylamine, t-butylamine, N' -dibenzylethylenediamine, procaine, chloroprocaine, choline, diethanolamine, ethylenediamine, N-methylglucamine, and the like.
Additional aspects and advantages of the application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the application.
Detailed Description
The following detailed description of embodiments of the present application is exemplary and intended to be used to explain the present application and should not be taken as limiting the present application.
In the application, the disclosure of numerical ranges includes disclosure of all values and further sub-ranges within the entire range, including endpoints and sub-ranges given for these ranges.
In the application, the related raw materials, equipment and the like are all raw materials and equipment which can be self-made by commercial paths or known methods unless specified otherwise; the methods involved, unless otherwise specified, are all conventional.
In the present application, the abbreviations for the functional groups have the meanings shown in Table 1:
TABLE 1 abbreviations for functional groups and their meanings
Definition of chiral phosphoric acid formula (I)
Wherein R is 1 、R 2 Are allIn the case of the formula (I) -1, R 1 、R 2 Are all->In the case of the formula (I) -2, R 1 、R 2 The case of the homophenyl (Ph) is of the formula (I) -3, R 1 、R 2 Are all->In the case of the formula (I) -4, R 1 、R 2 Are allThe case of (C) is represented by the formula (I) -5.
The nuclear magnetic resonance fluorine spectra in the following examples of the present application are all 13 C spectrum.
Example 1 (template reaction)
Into a dried 10mL schlenk tube was added (III) -1 (0.1 mmol,1.0 eq.) ZrCl 4 (0.005 mmol,5 mol%) and (I) -1 (0.015 mmol,15 mol%); (IV) -1 (0.2 mmol,2.0 eq.) was then dissolved in dry CHCl 3 (0.2 mL) and was placed in a schlenk tube using a syringe, and the resulting mixture was subjected to three times of freeze-aeration-thawing and degassing processes, so that the gas in the system was completely replaced with nitrogen, and a solid was formed in the reaction tube, which was an intermediate (R) represented by the formula (II) -1 3 ＝Ph，R 4 =me), from (III) -1, zrCl 4 And (I) -1. The reaction tube was placed at a distance of about 1cm from the 10W 400nm LED light source, and the reaction system was irradiated for 2 hours while stirring (i.e., the reaction time was 2 hours). At this time, the solid in the reaction tube disappeared, and the solution was directly purified by silica gel column chromatography to obtain the main product (V) -1, which was the target product with a yield of 90% and an ee value of 91%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.88 (dd, j=7.7, 1.7hz, 2H), 7.55 (t, j=7.4 hz, 1H), 7.44 (t, j=7.6 hz, 2H), 4.91 (dd, j=8.2, 6.0hz, 1H), 2.60 (dt, j=12.1, 6.0hz, 1H), 2.57-2.50 (m, 2H), 2.16 (s, 3H), 2.14-2.06 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 207.34,195.96,135.63,133.45,128.84,128.22,42.50,40.58,29.95,23.87; nuclear magnetic resonance fluorine spectrum (376 mhz, deuterated chloroform) δ -140.92-141.25 (m), -154.26 (t, j=20.9 Hz), -160.78-160.99 (m).
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=10:90, flow rate=1.0 mL/min, wavelength=240 nm, retention time 12.30min (major), 10.13min (minor), specific optical rotation [ α] D 25 ＝+4.2(c＝3.31,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2919,2850,1715,1692,1654,1597,1521,1499,1448,1369,1298,1264,1224,1161,1123,1059,980,940,893,852,774,700,661。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 18 H 14 O 2 F 5 + 357.0908,found 357.0909。
Example 2 (intermediate equivalent reaction)
Into a dry 50mL round bottom flask was added (III) -1 (5 mmol,1.0 eq.) ZrCl 4 (0.025 mmol,5 mol%) and (I) -1 (0.075 mmol,15 mol%) and drying CHCl 3 (1.0 mL) was added to the flask by syringe, and stirred at room temperature for 2 minutes, at which time a solid was formed in the flask, which was the intermediate (R) represented by the formula (II) -1 3 ＝Ph，R 4 =me), from (III) -1, zrCl 4 And (I)) -1 formation; after separating the solids by suction filtration, (II) -1 (0.1 mmol,1.0 eq.) is added to a dry 10mL schlenk tube and (IV) -1 (0.2 mmol,2.0 eq.) is then dissolved in dry CHCl 3 (0.2 mL) and adding the mixture into a schlenk tube by a syringe, and performing three times of operations by freezing, ventilation, thawing and degassing to completely change the gas in the system into nitrogen, placing the reaction tube at a position about 1cm away from 10W 400nm LED light source, irradiating the reaction system for 2H while stirring, and adding H 2 O (2 mmol,20.0 eq). The solution was directly purified by silica gel column chromatography to give the main product (V) -1 as the objective product in 85% yield and 80% ee.
Example 3 (intermediate catalyzed reaction)
Into a dry 50mL round bottom flask was added (III) -1 (5 mmol,1.0 eq.) ZrCl 4 (0.025 mmol,5 mol%) and (I) -1 (0.075 mmol,15 mol%) and drying CHCl 3 (1.0 mL) was placed in the flask with a syringe, and stirred at room temperature for 2 minutes, at which time a solid was formed in the flask, which was an intermediate (R) represented by the formula (II) -1 3 ＝Ph，R 4 =me), from (III) -1, zrCl 4 And (I) -1; after separating the solid by suction filtration, add (III) -1 (0.1 mmol,1.0 eq.) to a dry 10mL schlenk tube, add (II) -1 (0.005 mmol,5 mol%) and then dissolve (IV) -1 (0.2 mmol,2.0 eq.) in dry CHCl 3 (0.2 mL) and was placed in a schlenk tube with a syringe, and the resulting mixture was subjected to three times of operations by freeze-aeration-defrosting and degassing process so that the gas in the system was completely replaced with nitrogen gas, the reaction tube was placed at a distance of about 1cm from a 10W 400nm LED light source, and the reaction system was irradiated for 2 hours while stirring. At this time, the solid in the reaction tube disappeared, and the solution was directly purified by silica gel column chromatography to obtain the main product (V) -1, which was the target product with a yield of 88% and an ee value of 91%.
Example 4 (intermediate equivalent reaction)
Into a dry 50mL round bottom flask was added (III) -18 (5 mmol,1.0 eq.) ZrCl 4 (0.025 mmol,5 mol%) and (I) -1 (0.075 mmol,15 mol%) and drying CHCl 3 (1.0 mL) was placed in the flask with a syringe, and stirred at room temperature for 2 minutes, at which time a solid was formed in the flask, which was an intermediate represented by the formula (II) -2(R 3 ＝R 4 =ph), from (III) -18, zrCl 4 After separation of the solid by suction filtration, the solid was added to a dry 10mL schlenk tube (II) -2 (0.1 mmol,1.0 eq.) and (IV) -1 (0.2 mmol,2.0 eq.) was dissolved in dry CHCl 3 (0.2 mL) and was placed in a schlenk tube with a syringe, the resulting mixture was subjected to three times of freeze-aeration-thawing and degassing to allow the total gas in the system to be replaced with nitrogen, the reaction tube was placed at a distance of about 1cm from a 10W 400nm LED light source, the reaction system was irradiated for 2 hours while stirring, and H was added 2 O (2 mmol,20.0 eq). The solution was directly purified by silica gel column chromatography to give the main product (V) -24 as the objective product in a yield of 81% and an ee value of 76%.
Example 5 (intermediate catalyzed reaction)
Into a dry 50mL round bottom flask was added (III) -18 (5 mmol,1.0 eq.) ZrCl 4 (0.025 mmol,5 mol%) and (I) -1 (0.075 mmol,15 mol%) and drying CHCl 3 (1.0 mL) was added to the flask by syringe, and stirred at room temperature for 2min, at which time a solid was formed in the flask, which was an intermediate (R) represented by the formula (II) -2 3 ＝R 4 =ph), from (III) -18, zrCl 4 And (I) -1; after separating the solid by suction filtration, (III) -18 (0.1 mmol,1.0 eq.) and (II) -2 (0.005 mmol,5 mol%) were added to a dry 10mL schlenk tube, and (IV) -1 (0.2 mmol,2.0 eq.) was dissolved in dry CHCl 3 (0.2 mL) and was placed in a schlenk tube with a syringe, and the resultant mixture was subjected to three times of operations by freeze-aeration-defrosting and deaeration so that the gas in the system was completely replaced with nitrogen, and the reaction tube was placed at a distance of about 1cm from a 10W 400nm LED light source, and the reaction system was irradiated for 2 hours while stirring. At this time, the solid in the reaction tube disappeared, and the solution was directly purified by silica gel column chromatography to obtain the main product, which was the target product (V) -24, in 86% yield with an ee value of 81%.
Example 6
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -2,1, 5-dicarbonyl compound is shown as a formula (V) -2; the reaction time is 3h; the desired product was obtained as (V) -2 in a yield of 90% and an ee value of 81%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) δ 7.87 (dd, j=8.4, 1.3hz, 2H), 7.56-7.50 (m, 1H), 7.42 (dd, j=8.4, 7.0hz, 2H), 4.91 (dd, j=8.4, 6.2hz, 1H), 2.68-2.54 (m, 1H), 2.49 (t, j=6.7 hz, 2H), 2.40 (q, j=7.4 hz, 2H), 2.20-2.03 (m, 1H), 1.05 (t, j=7.3 hz, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 210.16,196.01,135.65,133.42,128.84,128.24,42.60,39.22,35.98,23.94,7.76.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=243 nm, retention time 11.76min (major), 7.50min (minor), specific optical rotation [ α] D 25 ＝+12.1(c＝1.96,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2977,2938,2855,1712,1692,1655,1597,1521,1499,1448,1375,1297,1261,1223,1118,994,959,910,856,768,699,662。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 19 H 16 O 2 F 5 + 371.1065,found 371.1064。
Example 7
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -3,1,5-dicarbonyl compound is shown in the formula (V) -3; the reaction time is 3h; the desired product was obtained as (V) -3 in 79% yield with an ee value of 80%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.91-7.84 (m, 2H), 7.56-7.50 (m, 1H), 7.42 (t, j=7.7 hz, 2H), 4.91 (dd, j=8.4, 6.2hz, 1H), 2.58 (dt, j=13.6, 6.6hz, 1H), 2.53-2.45 (m, 2H), 2.35 (t, j=7.3 hz, 2H), 2.16-2.03 (m, 1H), 1.69-1.50 (m, 2H), 0.90 (t, j=7.4 hz, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 209.71,196.02,135.66,133.42,128.83,128.24,44.77,42.60,39.64,23.89,17.25,13.66.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=243 nm, retention time 8.77min (major), 7.47min (minor), specific optical rotation [ α ] D 25 ＝+9.9(c＝2.28,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2963,2933,2877,1709,1693,1597,1521,1499,1448,1374,1296,1261,1221,1123,992,963,770,699,661,609。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 20 H 18 O 2 F 5 + 185.1221,found 385.1219。
Example 8
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -4,1,5-dicarbonyl compound is shown in the formula (V) -4; the reaction time is 2.5h; the desired product was obtained as (V) -4 in 80% yield with an ee value of 90%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 7.95-7.81 (m, 2H), 7.57-7.50 (m, 1H), 7.43 (dd, j=8.4, 7.0hz, 2H), 4.93 (dd, j=8.4, 5.9hz, 1H), 2.69-2.44 (m, 4H), 2.19-1.99 (m, 1H), 1.07 (d, j=6.9 hz, 6H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 213.51,196.08,135.66,133.42,128.84,128.27,42.59,40.86,37.23,23.91,18.21 (d, j=2.6 Hz).
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=243 nm, retentionTime 6.67min (major), 5.64min (minor) specific optical rotation [ alpha ]] D 25 ＝-9.6(c＝2.18,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2971,2932,2876,1693,1655,1597,1521,1499,1448,1384,1368,1261,1224,1124,990,959,778,699,662。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 20 H 18 O 2 F 5 + 385.1221,found 385.1220。
Example 9
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -5,1,5-dicarbonyl compound is shown in the formula (V) -5; the reaction time is 10h; the desired product was obtained as (V) -5 in 88% yield with an ee value of 14%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.96-7.85 (m, 2H), 7.57-7.49 (m, 1H), 7.47-7.39 (m, 2H), 4.95 (dd, j=8.6, 5.5hz, 1H), 2.66-2.50 (m, 3H), 2.18-1.99 (m, 1H), 1.10 (s, 9H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 214.88,196.13,135.69,133.39,128.82,128.29,44.09,42.57,33.54,26.40,24.15.
High performance liquid chromatography analysis Daicel Chiralpak IC-H, isopropanol/n-hexane=2:98, flow rate=0.5 mL/min, wavelength=242 nm, retention time 20.91min (major), 19.51min (minor), specific optical rotation [ α] D 25 ＝+0.9(c＝2.27,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2969,236,2912,1872,1698,1655,1597,1521,1500,1448,1367,1288,1223,1123,1047,994,963,925,861,764,698,661,614。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 21 H 20 O 2 F 5 + 399.1378,found 399.1376。
Example 10
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -6,1,5-dicarbonyl compound is shown in the formula (V) -6; the reaction time is 0.5h; the desired product was obtained as (V) -6 in 99% yield with an ee value of 69%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.86 (d, j=8.9 hz, 2H), 6.89 (d, j=8.9 hz, 2H), 4.84 (dd, j=8.1, 6.0hz, 1H), 3.83 (s, 3H), 2.67-2.43 (m, 3H), 2.13 (s, 3H), 2.11-2.02 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 207.48,194.25,163.75,130.61,128.40,114.03,55.48,42.14,40.68,29.95,23.99.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=272 nm, retention time 23.53min (major), 11.91min (minor), specific optical rotation [ α] D 25 ＝-5.8(c＝2.94,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2955,2921,2849,1715,1682,1599,1576,1521,1498,1420,1367,1311,1258,1170,1121,1029,980,893,841,755,613,592,513.。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 19 H 16 O 3 F 5 + 387.1014,found 387.1011。
Example 11
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -7, and the structure of the 1, 5-dicarbonyl compound is shown as a formula (V) -7; the reaction time is 0.5h; the desired product was obtained as (V) -7 in 94% yield with an ee value of 87%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.75 (d, j=8.3 hz, 2H), 7.21 (d, j=8.0 hz, 2H), 4.85 (dd, j=8.1, 6.0hz, 1H), 2.63-2.47 (m, 3H), 2.37 (s, 3H), 2.13 (s, 3H), 2.10-2.03 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 207.34,195.49,144.39,133.09,129.52,128.34,42.39,40.65,29.91,23.92,21.59.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=252 nm, retention time 14.92min (major), 7.44min (minor), specific optical rotation [ α] D 25 ＝-1.2(c＝2.59,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2925,2855,1715,1688,1607,1521,1498,1410,1369,1263,1229,1183,1161,1122,979,893,826,789,754,612,479。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 19 H 16 O 2 F 5 + 371.1065,found 371.1063。
Example 12
This embodiment is substantially the same as embodiment 1 except that:
The structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -8,1,5-dicarbonyl compound is shown in the formula (V) -8; the reaction time is 2h; the desired product was obtained as (V) -8 in 96% yield with an ee value of 15%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.86-7.78 (m, 2H), 7.47-7.41 (m, 2H), 4.87 (dd, j=8.1, 6.1hz, 1H), 2.68-2.46 (m, 3H), 2.13 (s, 3H), 2.10-2.04 (m, 1H), 1.30 (s, 9H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 207.40,195.29,157.36,132.85,128.28,125.84,42.32,40.67,35.15,30.98,29.94,23.97.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=252 nm, retention time 6.32min (major), 9.86min (minor), specific optical rotation [ α] D 25 ＝+1.6(c＝2.89,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2964,2908,1871,1716,1688,1604,1521,1498,1408,1365,1267,122,1191,1161,1109,1059,980,893,846,747,708,630,594,558。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 22 H 22 O 2 F 5 + 413.1534,found 413.1531。
Example 13
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -9,1,5-dicarbonyl compound is shown in the formula (V) -9; the reaction time is 2h; the desired product was obtained as (V) -9 in 75% yield with an ee value of 4%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.98 (d, j=8.2 hz, 2H), 7.69 (d, j=8.2 hz, 2H), 4.91 (dd, j=8.5, 5.6hz, 1H), 2.56 (ttd, j=14.9, 8.0,6.9,3.7hz, 3H), 2.14 (s, 3H), 2.08 (q, j=7.3, 6.0hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 207.20,195.20,138.39,134.71 (q, j=32.7 Hz), 128.58,125.94 (q, j=3.7 Hz), 42.80,40.26,29.96,29.69,23.72.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=254 nm, retention time 5.92min (major), 7.79min (minor), specific optical rotation [ α] D 25 ＝+3.0(c＝1.31,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2955,2921,2852,1715,1701,1522,1500,1410,1323,1167,1126,1067,981,893,859,752,599,511。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 19 H 13 O 2 F 8 + 425.0782,found 425.0780。
Example 14
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -10,1,5-dicarbonyl compound is shown in the formula (V) -10; the reaction time is 1.5h; the desired product was obtained as (V) -10 in 95% yield with an ee value of 93%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.01-7.83 (m, 2H), 7.10 (t, j=8.6 hz, 2H), 4.86 (dd, j=8.4, 5.7hz, 1H), 2.71-2.43 (m, 3H), 2.13 (s, 3H), 2.11-2.02 (m, 1H); nuclear magnetic resonance carbon spectra (101 mhz, deuterated chloroform) δ 207.35,194.37,165.83 (d, j= 255.9 Hz), 131.92 (d, j=2.7 Hz), 130.97 (d, j=9.3 Hz), 116.05 (d, j=22.0 Hz), 42.45,40.44,29.96,23.87.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=246 nm, retention time 9.29min (major), 6.60min (minor), specific optical rotation [ α] D 25 ＝-1.6(c＝3.67,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3077,2925,2854,1715,1693,1597,1521,1498,1410,1369,1230,1158,1123,1059,981,893,845,752,610,507,431。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H ] + Calcd for C 18 H 13 O 2 F 6 + 375.0814,found 375.0811。
Example 15
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -11,1,5-dicarbonyl compound is shown in the formula (V) -11; the reaction time is 1h; the desired product was obtained as (V) -11 in 92% yield with an ee value of 95%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.05-7.86 (m, 2H), 7.19-7.02 (m, 2H), 4.89 (dd, j=8.6, 5.9hz, 1H), 2.64-2.54 (m, 1H), 2.54-2.43 (m, 2H), 2.40 (qd, j=7.4, 1.2hz, 2H), 2.15-2.03 (m, 1H), 1.05 (t, j=7.3 hz, 3H); nuclear magnetic resonance carbon spectra (101 mhz, deuterated chloroform) δ 210.21,194.44,165.83 (d, j= 255.8 Hz), 131.92 (d, j=3.2 Hz), 131.00 (d, j=9.3 Hz), 116.05 (d, j=21.9 Hz), 42.55,39.08,36.00,23.93,7.76.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=245 nm, retention time 8.74min (major), 6.49min (minor), specific optical rotation [ α] D 25 ＝-1.4(c＝2.50,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2979,2939,2921,2851,1713,1693,1597,1521,1499,1411,1298,1230,1158,1120,995,960,911,847,741,603,506。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 19 H 15 O 2 F 6 + 389.0971,found 389.0971。
Example 16
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -12,1,5-dicarbonyl compound is shown in the formula (V) -12; the reaction time is 1.5h; the desired product was obtained as (V) -12 in 93% yield with an ee value of 90%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.98-7.87 (m, 2H), 7.18-7.04 (m, 2H), 4.89 (dd, j=8.6, 6.0hz, 1H), 2.62-2.52 (m, 1H), 2.50-2.40 (m, 2H), 2.35 (t, j=7.4 hz, 2H), 2.14-2.03 (m, 1H), 1.58 (q, j=7.4 hz, 2H), 0.90 (t, j=7.4 hz, 3H); nuclear magnetic resonance carbon spectra (101 mhz, deuterated chloroform) δ 209.78,194.44,165.83 (d, j= 255.8 Hz), 131.92 (d, j=3.1 Hz), 131.00 (d, j=9.4 Hz), 116.05 (d, j=22.0 Hz), 44.78,42.55,39.50,23.88,17.24,13.65.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanolN-hexane=5:95, flow rate=1.0 mL/min, wavelength=245 nm, retention time: 7.85min (major), 6.37min (minor), specific optical rotation [ α] D 25 ＝-2.8(c＝3.13,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2964,2935,2878,1693,1597,1521,1499,1410,1373,1298,1234,1158,1123,995,964,843,750,603,507。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 20 H 17 O 2 F 6 + 403.1127,found 403.1123。
Example 17
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -13,1,5-dicarbonyl compound is shown in the formula (V) -13; the reaction time is 1.5h; the desired product was obtained as (V) -13 in 88% yield with an ee value of 92%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.03-7.91 (m, 2H), 7.17-7.03 (m, 2H), 4.91 (dd, j=8.7, 5.5hz, 1H), 2.67-2.41 (m, 4H), 2.17-2.03 (m, 1H), 1.07 (dd, j=7.0, 2.0hz, 6H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 213.52,194.47,165.84 (d, j= 255.9 Hz), 131.94 (d, j=3.0 Hz), 131.03 (d, j=9.3 Hz), 116.03 (d, j=22.0 Hz), 42.55,40.86,37.10,23.91,18.20 (d, j=3.6 Hz).
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=245 nm, retention time 6.23min (major), 5.70min (minor), specific optical rotation [ α] D 25 ＝-7.3(c＝1.35,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2972,2931,276,2854,1694,1597,1521,1499,409,1298,1231,1158,1124,994,963,847,765,603,506。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 20 H 17 O 2 F 6 + 403.1127,found 403.1124。
Example 18
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -14,1,5-dicarbonyl compound is shown in the formula (V) -14; the reaction time is 0.5h; the desired product was obtained as (V) -14 in 87% yield and 91% ee.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.91-7.76 (m, 2H), 7.44-7.35 (m, 2H), 4.85 (dd, j=8.4, 5.6hz, 1H), 2.67-2.43 (m, 3H), 2.13 (s, 3H), 2.12-2.01 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 207.31,194.83,139.97,133.88,129.65,129.21,42.51,40.40,29.96,23.80.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=253 nm, retention time 12.08min (major), 6.86min (minor), specific optical rotation [ α] D 25 ＝+4.2(c＝2.37,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2926,2872,2855,1715,1693,1590,1521,1499,1400,1369,1262,122,1161,1122,1092,1059,981,893,849,750,593,553,531,480。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 18 H 13 O 2 F 5 Cl + 391.0519,found 391.0514。
Example 19
This embodiment is substantially the same as embodiment 1 except that:
The structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -15,1,5-dicarbonyl compound is shown in the formula (V) -15; the reaction time is 0.5h; the desired product was obtained as (V) -15 in a yield of 90% and an ee value of 80%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 7.81-7.69 (m, 2H), 7.61-7.47 (m, 2H), 4.84 (dd, j=8.4, 5.7hz, 1H), 2.67-2.41 (m, 3H), 2.13 (s, 3H), 2.11-1.97 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 207.25,195.03,134.33,132.20,129.71,128.68,42.50,40.39,29.94,23.80.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=257 nm, retention time 15.84min (major), 7.63min (minor), specific optical rotation [ α] D 25 ＝+3.9(c＝3.27,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2925,2854,1715,1693,1585,1521,1499,1396,1370,1262,1221,1162,1124,1071,980,893,848,764,593,548,11,473。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 18 H 13 O 2 F 5 Br + 435.0014,found 435.0012。
Example 20
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -16,1,5-dicarbonyl compound is shown in the formula (V) -16; the reaction time is 1.5h; the desired product was obtained as (V) -16 in 92% yield with an ee value of 85%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) δ 7.76 (td, j=7.5, 1.9hz, 1H), 7.46 (dddd, j=8.3, 7.2,5.1,1.9hz, 1H), 7.21 (td, j=7.6, 1.1hz, 1H), 7.01 (ddd, j=11.1, 8.3,1.1hz, 1H), 4.69 (dd, j=8.5, 5.1hz, 1H), 2.53 (dddd, j=20.5, 15.8,8.0,5.1hz, 3H), 2.13 (s, 3H), 2.07-1.98 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 207.07,194.91,160.47 (d, j=252.8 Hz), 134.72 (d, j=9.0 Hz), 131.04 (d, j=2.9 Hz), 124.91 (d, j=3.3 Hz), 124.77,116.33 (d, j=23.5 Hz), 46.98 (d, j=6.0 Hz), 40.76,29.89,23.81.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=235 nm, retention time 9.36min (major), 7.63min (minor), specific optical rotation [ α] D 25 ＝+2.8(c＝2.54,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2921,2850,1715,1695,1610,1521,1499,1452,136,1276,1215,1162,1125,1048,981,894,765,641,533,456。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 18 H 13 O 2 F 6 + 375.0814,found 375.0810。
Example 21
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -17,1,5-dicarbonyl compound is shown in the formula (V) -17; the reaction time is 2h; the desired product was obtained as (V) -17 in a yield of 90% and an ee value of 77%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.62 (dt, j=7.9, 1.3hz, 1H), 7.56 (ddd, j=9.3, 2.7,1.6hz, 1H), 7.40 (td, j=8.0, 5.5hz, 1H), 7.22 (tdd, j=8.1, 2.7,1.0hz, 1H), 4.85 (dd, j=8.4, 5.6hz, 1H), 2.66-2.46 (m, 3H), 2.13 (s, 3H), 2.11-2.01 (m, 1H); nuclear magnetic resonance carbon spectra (101 mhz, deuterated chloroform) δ 207.19,194.76,162.86 (d, j=248.7 Hz), 137.67 (d, j=6.2 Hz), 130.53 (d, j=7.6 Hz), 123.84 (d, j=2.9 Hz), 120.51 (d, j=21.3 Hz), 115.14 (d, j=22.6 Hz), 42.70,40.37,29.88,23.81.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=239 nm, retention time 11.27min (major), 7.15min (minor), specific optical rotation [ α ] D 25 ＝-4.6(c＝2.01,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3075,2928,2857,1715,1697,1588,1521,1499,1441,1370,1265,1154,1122,982,881,815,787,739,676,446。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 18 H 13 O 2 F 6 + 375.0814,found 375.0811。
Example 22
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -10, the structure of the olefin compound is shown as a formula (IV) -2,1, 5-dicarbonyl compound is shown as a formula (V) -18; the reaction time is 2h; the desired product was obtained as (V) -18 in 83% yield and 79% ee.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.04-7.93 (m, 2H), 7.37-7.20 (m, 5H), 7.09-6.99 (m, 2H), 4.64-4.56 (m, 1H), 2.45-2.39 (m, 2H), 2.37 (ddd, j=7.8, 6.0,1.7hz, 1H), 2.17-2.10 (m, 1H), 2.09 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 208.46,197.94,165.56 (d, j=255.0 Hz), 138.87,132.96 (d, j=3.2 Hz), 131.41 (d, j=9.2 Hz), 129.13,128.24,127.37,115.64 (d, j=21.9 Hz), 52.20,40.83,30.01,27.58.
High performance liquid chromatography analysis Daicel Chiralpak IC-H, isopropanol/n-hexane=30:70, flow rate=1.0 mL/min, wavelength=246 nm, retention time 10.67min (major), 13.78min (minor), specific optical rotation [ α] D 25 ＝-3.2(c＝1.81,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3064,3028,2928,2855,1712,1679,1596,1506,1453,1409,1366,1268,1231,1156,976,845,762,702,595,522。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 18 H 18 O 2 F + 285.1285,found 285.1282。
Example 23
This embodiment is substantially the same as embodiment 1 except that:
The structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -10, the structure of the olefin compound is shown as a formula (IV) -3,1,5-dicarbonyl compound is shown as a formula (V) -19; the reaction time is 1h; the desired product was obtained as (V) -19 in 77% yield with an ee value of 84%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.01-7.93 (m, 2H), 7.16-7.08 (m, 4H), 7.03 (t, j=8.6 hz, 2H), 4.56 (dd, j=7.7, 6.4hz, 1H), 2.47-2.37 (m, 2H), 2.37-2.31 (m, 1H), 2.28 (s, 3H), 2.14-2.03 (m, 4H); nuclear magnetic resonance carbon spectra (101 mhz, deuterated chloroform) δ 208.50,198.06,165.52 (d, j= 254.8 Hz), 137.05,135.78,133.03 (d, j=2.9 Hz), 131.38 (d, j=9.3 Hz), 129.82,128.10,115.59 (d, j=21.9 Hz), 51.85,40.87,29.97,27.54,21.01.
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=3:97, flow rate=1.0 mL/min, wavelength=244 nm, retention time 25.38min (major), 21.28min (minor), specific optical rotation [ α] D 25 ＝-48.8(c＝1.79,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2955,2924,2855,1712,1679,1595,1506,1408,1363,1266,1230,1155,975,846,815,787,750,659,594,547,514。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 19 H 19 O 2 F + 299.1442,found 299.1438。
Example 24
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -10, the structure of the olefin compound is shown as a formula (IV) -4,1,5-dicarbonyl compound is shown as a formula (V) -20; the reaction time is 1.5h; the desired product was obtained as (V) -20 in a yield of 81% and an ee value of 83%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.00-7.93 (m, 2H), 7.25-7.19 (m, 2H), 7.10-7.02 (m, 2H), 7.02-6.95 (m, 2H), 4.62 (dd, j=8.1, 6.2hz, 1H), 2.45-2.37 (m, 2H), 2.37-2.31 (m, 1H), 2.09 (s, 3H), 2.07-1.98 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 208.30 (d, j=2.6 Hz), 197.91,165.66 (d, j= 255.3 Hz), 162.04 (d, j=246.5 Hz), 134.55 (d, j=3.3 Hz), 132.81 (d, j=2.7 Hz), 131.37 (d, j=9.3 Hz), 129.80 (d, j=8.1 Hz), 116.01 (d, j=21.6 Hz), 115.73 (d, j=21.8 Hz), 51.18,40.68,30.00,27.67.
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=246 nm, retention time 26.92min (major), 20.48min (minor), specific optical rotation [ α] D 25 ＝-18.4(c＝1.39,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2957,2925,2853,1712,1680,1595,1506,1409,1363,1224,1155,1100,1013,833,793,704,607,547,516,431。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 18 H 17 O 2 F 2 + 303.1191,found 303.1189。
Example 25
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -10, the structure of the olefin compound is shown as a formula (IV) -5,1,5-dicarbonyl compound is shown as a formula (V) -21; the reaction time is 1h; the desired product was obtained as (V) -21 in a yield of 90% and an ee value of 92%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.00-7.93 (m, 2H), 7.30-7.26 (m, 2H), 7.22-7.17 (m, 2H), 7.10-7.03 (m, 2H), 4.62 (t, j=7.1 hz, 1H), 2.47-2.39 (m, 2H), 2.39-2.31 (m, 1H), 2.09 (s, 3H), 2.08-2.01 (m, 1H); nuclear magnetic resonance carbon spectra (101 mhz, deuterated chloroform) δ 208.21,197.65,165.68 (d, j= 255.4 Hz), 137.31,133.32,132.74 (d, j=2.1 Hz), 131.35 (d, j=9.3 Hz), 129.58,129.27,115.75 (d, j=21.9 Hz), 51.30,40.60,30.00,27.52.
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=3:97, flow rate=1.0 mL/min, wavelength=245 nm, retention time 28.58min (major), 24.16min (minor), specific optical rotation [ α] D 25 ＝-9.7(c＝2.35,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2956,2925,2853,1712,1679,1595,1506,1491,1409,1363,1231,1156,1092,1014,819,784,750,692,607,531,504。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 18 H 16 O 2 FCl + 319.0896,found 319.0894。
Example 26
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -10, the structure of the olefin compound is shown as a formula (IV) -6,1,5-dicarbonyl compound is shown as a formula (V) -22; the reaction time is 1h; the desired product was obtained as (V) -22 in 80% yield with an ee value of 88%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.11-7.93 (m, 2H), 7.58 (d, j=8.1 hz, 2H), 7.41 (d, j=8.1 hz, 2H), 7.14-7.05 (m, 2H), 4.75 (t, j=7.1 hz, 1H), 2.49-2.37 (m, 3H), 2.17-2.05 (m, 4H); nuclear magnetic resonance carbon spectra (101 mhz, deuterated chloroform) δ 208.09,197.37,165.80 (d, j= 255.8 Hz), 142.90,132.67 (d, j=2.5 Hz), 131.39 (d, j=9.4 Hz), 129.71 (q, j=32.5 Hz), 128.65,126.02 (q, j=3.8 Hz), 115.86 (d, j=22.0 Hz), 51.67,40.55,30.01,27.62.
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=3:97, flow rate=1.0 mL/min, wavelength=248 nm, retention time 18.01min (major), 15.31min (minor), specific optical rotation [ α ] D 25 ＝-3.9(c＝1.68,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )2957,2926,2854,1714,1681,1596,1507,1410,1323,1157,1111,1068,1018,836,751,685,607,525。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 19 H 17 O 2 F 4 + 353.1159,found 353.1155。
Example 27
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -10, the structure of the olefin compound is shown as a formula (IV) -7,1, 5-dicarbonyl compound is shown as a formula (V) -23; the reaction time is 1.5h; the desired product was obtained as (V) -23 in 80% yield with an ee value of 81%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.06-7.90 (m, 2H), 7.19 (td, j=9.1, 8.7,6.3hz, 1H), 7.12-7.00 (m, 2H), 6.88-6.75 (m, 2H), 4.97-4.84 (m, 1H), 2.51-2.30 (m, 3H), 2.10 (s, 3H), 2.07-1.94 (m, 1H); nuclear magnetic resonance carbon spectra (101 mhz, deuterated chloroform) δ 207.71,197.18,165.83 (d, j=255.5 Hz), 163.75-161.16 (m), 161.07-158.33 (m), 132.40,131.17 (d, j=9.4 Hz), 129.91 (dd, j=9.6, 5.2 Hz), 121.76 (d, j=11.8 Hz), 115.84 (d, j=22.0 Hz), 112.22 (dd, j=21.3, 3.7 Hz), 104.10 (t, j=26.2 Hz), 43.01,40.57,29.91,26.62.
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=248 nm, retention time 21.77min (major), 25.62min (minor), specific optical rotation [ α] D 25 ＝-2.3(c＝1.68,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3077,2927,1855,1714,1683,1595,1502,1410,1367,1275,1231,1156,1139,1095,965,846,816,750,611,561,505,468,427。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 18 H 16 O 2 F 3 + 321.1097,found 321.1093。
Example 28
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown in the formula (III) -18,1,5-dicarbonyl compound is shown in the formula (V) -24; the reaction time is 1h; the desired product was obtained as (V) -24 in a yield of 90% and an ee value of 81%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.92 (t, j=8.7 hz, 4H), 7.61-7.50 (m, 2H), 7.44 (q, j=8.2 hz, 4H), 5.04 (t, j=7.3 hz, 1H), 3.09 (t, j=6.8 hz, 2H), 2.78 (dq, j=14.0, 7.0hz, 1H), 2.30 (dq, j=14.0, 6.9hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 198.86,196.05,136.53,135.61,133.42,133.29,128.82,128.64,128.24,127.91,42.63,35.65,24.40.
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=10:90, flow rate=1.0 mL/min, wavelength=242 nm, retention time 10.13min (major), 12.30min (minor), specific optical rotation [ α] D 25 ＝-19.1(c＝2.96,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3359,3062,2936,2641,2422,1967,1688,1655,1597,1581,1522,1501,1149,1273,1221,1182,1124,1001,970,948,864,847,723,700,661。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 23 H 16 O 2 F 5 + 419.1065,found 419.1061。
Example 29
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -18, the structure of the olefin compound is shown as a formula (IV) -2,1, 5-dicarbonyl compound is shown as a formula (V) -25; the reaction time is 1h; the desired product was obtained as (V) -25 in 95% yield with an ee value of 70%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.01-7.97 (m, 2H), 7.94-7.88 (m, 2H), 7.53 (d, j=7.4 hz, 1H), 7.50-7.36 (m, 5H), 7.35-7.25 (m, 4H), 7.24-7.19 (m, 1H), 4.79 (t, j=7.3 hz, 1H), 2.98 (qt, j=17.2, 6.9hz, 2H), 2.60 (dq, j=14.3, 7.2hz, 1H), 2.39-2.21 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.85,199.57,139.11,136.77,136.59,132.99,132.88,129.00,128.73,128.51,128.47,128.28,127.98,127.18,52.40,35.93,28.26.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=241 nm, retention time 19.93min (major), 24.04min (minor), specific optical rotation [ α] D 25 ＝-80.5(c＝2.84,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3060,3026,2933,1681,1597,1580,1492,447,1409,1367,1275,1222,1178,1001,980,751,734,698,568,518。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 23 H 21 O 2 + 329.1536,found 329.1532。
Example 30
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -18, the structure of the olefin compound is shown as a formula (IV) -3,1,5-dicarbonyl compound is shown as a formula (V) -26; the reaction time is 1h; the desired product was obtained as (V) -26 in 93% yield with an ee value of 66%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.99 (d, j=7.5 hz, 2H), 7.95-7.87 (m, 2H), 7.54 (t, j=7.4 hz, 1H), 7.42 (dp, j=21.0, 7.5hz, 5H), 7.20 (d, j=7.8 hz, 2H), 7.10 (d, j=7.8 hz, 2H), 4.75 (t, j=7.3 hz, 1H), 3.11-2.85 (m, 2H), 2.58 (dd, j=14.0, 7.1hz, 1H), 2.28 (m, 4H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.92,199.69,136.82,136.79,136.62,136.02,132.97,132.82,129.71,128.73,128.50,128.45,128.15,127.99,52.02,35.96,28.22,20.98.
High performance liquid chromatography analysis Daicel Chiralpak AD-H, isopropanol/n-hexane=20:80, flow rate=1.0 mL/min, wavelength=241 nm, retention time 10.17min (major), 11.41min (minor), specific optical rotation [ α] D 25 ＝-75.2(c＝2.81,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3344,3058,3025,2924,2858,1683,1597,1580,1512,1448,1411,1366,1275,1223,1179,1112,1022,1001,979,806,750,729,670,557。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 24 H 23 O 2 + 343.1693,found 343.1691。
Example 31
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -18, the structure of the olefin compound is shown as a formula (IV) -4,1,5-dicarbonyl compound is shown as a formula (V) -27; the reaction time is 1h; the desired product was obtained as (V) -27 in 84% yield with an ee value of 75%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.03-7.94 (m, 2H), 7.95-7.84 (m, 2H), 7.59-7.50 (m, 1H), 7.50-7.46 (m, 1H), 7.45-7.36 (m, 4H), 7.28 (ddd, j=9.7, 5.9,3.2hz, 2H), 6.98 (t, j=8.6 hz, 2H), 4.80 (t, j=7.4 hz, 1H), 3.16-2.81 (m, 2H), 2.59 (dd, j=14.1, 7.1hz, 1H), 2.27 (dt, j=14.0, 6.9hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.70,199.52,161.90 (d, j=246.1 Hz), 136.69,136.40,134.79 (d, j=3.2 Hz), 133.05 (d, j=3.4 Hz), 129.83 (d, j=8.0 Hz), 128.67,128.54,127.93,115.97,115.76,51.36,35.75,28.27.
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=10: 90, flow rate=1.0 mL/min, wavelength=241 nm, retention time 25.77min (major), 18.48min (minor), specific optical rotation [ α] D 25 ＝-102.4(c＝1.87,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3347,3064,2932,2857,1967,1898,1683,1597,1580,1507,1448,1417,1367,1277,1224,1179,1158,1098,1074,1001,979,960,832,752,731,690,556,516。
High resolution mass spectrometry (APCI Source) calcd for C 23 H 19 O 2 F:346.1369,found 346.1372。
Example 32
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -18, the structure of the olefin compound is shown as a formula (IV) -8,1,5-dicarbonyl compound is shown as a formula (V) -28; the reaction time is 1h; the desired product was obtained as (V) -28 in 88% yield with an ee value of 76%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.97 (d, j=7.7 hz, 2H), 7.90 (d, j=7.8 hz, 2H), 7.58-7.46 (m, 2H), 7.40 (dt, j=12.7, 7.8hz, 6H), 7.20 (d, j=8.2 hz, 2H), 4.79 (t, j=7.4 hz, 1H), 2.97 (dt, j=10.2, 6.9hz, 2H), 2.59 (dd, j=14.1, 7.1hz, 1H), 2.34-2.19 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.54,199.13,138.07,136.60,136.25,133.08,133.05,132.05,129.97,128.63,128.53,128.50,127.89,121.18,51.52,35.66,28.03.
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=240 nm, retention time 28.08min (major), 23.84min (minor), specific optical rotation [ α ] D 25 ＝-65.6(c＝2.72,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3346,3060,2959,2932,1967,1773,1683,1596,1580,1487,1448,1405,1367,1275,1222,1199,1178,1074,1011,1001,978,810,754,703,689,530。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 23 H 20 O 2 Br + 407.0641,found 407.0637。
Example 33
This embodiment is substantially the same as embodiment 1 except that:
the structure of the 1, 3-dicarbonyl compound is shown as a formula (III) -18, the structure of the olefin compound is shown as a formula (IV) -6,1,5-dicarbonyl compound is shown as a formula (V) -29; the reaction time is 1h; the desired product was obtained as (V) -29 in 85% yield with an ee value of 50%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.06-7.96 (m, 2H), 7.94-7.88 (m, 2H), 7.61-7.51 (m, 4H), 7.43 (ddd, j=17.7, 8.9,6.6hz, 6H), 4.91 (t, j=7.3 hz, 1H), 2.99 (q, j=6.9 hz, 2H), 2.63 (dq, j=14.2, 7.1hz, 1H), 2.29 (dq, j=13.8, 6.8hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.53,199.01,143.19,136.65,136.28,133.30,133.18,129.67,129.34,128.71,128.59,127.95,125.94 (q, j=3.8 Hz), 123.98 (d, j= 272.0 Hz), 51.92,35.69,28.21.
High performance liquid chromatography analysis Daicel Chiralpak OJ-H, isopropanol/n-hexane=5:95, flow rate=1.0 mL/min, wavelength=242 nm, retention time 15.49min (major), 12.90min (minor), specific optical rotation [ α] D 25 ＝-49.3(c＝1.49,CHCl 3 )。
Infrared spectrum (thin film, cm) -1 )3349,3062,2934,1922,1811,1683,1617,1597,1581,1449,1419,1367,1325,1277,11223,1166,1124,1069,1017,1001,977,831,752,728,699,666,610,569,528。
High resolution Mass Spectrometry (APCI Source) M/z: [ M+H] + Calcd for C 24 H 20 O 2 F 3 + 397.1410found 397.1407。
Example 34
Into a dried 10mL schlenk tube were added (VI) -1 (0.1 mmol,1.0 eq.) and biindene ZrCl 2 (CAS: 100080-82-8) (0.002 mmol,2 mol%), then (VII) -1 (0.2 mmol,2.0 eq.) was dissolved in dry DCM (1.0 mL) and added to the schlenk tube with a syringe, the resulting mixture was operated three times by freeze-air exchange-defrosting degasification process, allowing the gas in the system to be replaced with nitrogen gas all times, placing the reaction tube at about 1cm from the 10W 440nm LED light source and irradiating the reaction system for 2.5h (i.e., reaction time 2.5 h) while stirring. The solution is directly purified by silica gel column chromatography to obtain the main product (VIII) -1 with 99 percent of yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.01-7.97 (m, 2H), 7.94-7.88 (m, 2H), 7.53 (d, j=7.4 hz, 1H), 7.50-7.36 (m, 5H), 7.35-7.25 (m, 4H), 7.24-7.19 (m, 1H), 4.79 (t, j=7.3 hz, 1H), 2.98 (qt, j=17.2, 6.9hz, 2H), 2.60 (dq, j=14.3, 7.2hz, 1H), 2.39-2.21 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.85,199.57,139.11,136.77,136.59,132.99,132.88,129.00,128.73,128.51,128.47,128.28,127.98,127.18,52.40,35.93,28.26.
Infrared spectrum (thin film, cm) -1 )3060,3026,2933,1681,1597,1580,1492,447,1409,1367,1275,1222,1178,1001,980,751,734,698,568,518。
High resolution mass spectrometry (APCI Source) calcd for C 23 H 21 O 2 :329.1539,found 325.1539。
Example 35
This embodiment is substantially the same as embodiment 34 except that:
The olefin compound has a structure shown in a formula (VII) -2,1, 5-dicarbonyl compound has a structure shown in a formula (VIII) -2; the desired product was obtained as (VIII) -2 in 89% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 7.93 (dd, j=8.3, 1.4hz, 2H), 7.85 (dd, j=8.4, 1.3hz, 2H), 7.57-7.51 (m, 1H), 7.43 (dd, j=8.6, 7.1hz, 3H), 7.35 (dd, j=8.4, 7.0hz, 2H), 7.20 (d, j=6.9 hz, 1H), 7.15-7.06 (m, 3H), 4.93 (dd, j=8.8, 5.3hz, 1H), 3.12 (dt, j=17.3, 6.7hz, 1H), 3.01 (dt, j=17.3, 7.0hz, 1H), 2.55 (m, 4H), 2.18 (dtd, j=14.1, 7.1,5.3hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 200.33,200.07,137.96,136.95,136.82,135.38,133.02,132.80,131.12,128.55,128.50,128.43,128.03,127.28,127.10,126.63,48.69,36.26,27.63,19.76.
Infrared spectrum (thin film, cm) -1 )3345,3062,3025,2962,2930,1722,1683,1597,1580,1490,1448,1409,1365,1261,1222,1180,1100,1027,799,750,731,690,600,553,454。
High resolution mass spectrometry (APCI Source) calcd for C 24 H 23 O 2 :343.1693,found 343.1694。
Example 36
This embodiment is substantially the same as embodiment 34 except that:
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the olefin compound has a structure shown in the formula (VII) -3,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -3; the desired product was obtained as (VIII) -3 in 98% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.02-7.95 (m, 2H), 7.94-7.86 (m, 2H), 7.58-7.35 (m, 6H), 7.17 (d, j=7.8 hz, 1H), 7.10 (d, j=5.9 hz, 2H), 7.02 (d, j=7.5 hz, 1H), 4.73 (t, j=7.3 hz, 1H), 3.02 (dt, j=17.1, 7.2hz, 1H), 2.92 (dt, j=17.1, 6.7hz, 1H), 2.58 (dd, j=14.1, 7.1hz, 1H), 2.29 (m, 4H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 200.00,199.69,139.08,138.75,136.91,136.75,133.03,132.90,128.90,128.85,128.81,128.57,128.52,128.06,128.05,125.52,52.45,36.06,28.39,21.42.
Infrared spectrum (thin film, cm) -1 )3059,3026,2930,2861,1681,1597,1580,1489,1448,1366,1261,1213,1180,1094,1074,1057,1002,982,796,748,126,692。
High resolution mass spectrometry (APCI Source) calcd for C 24 H 23 O 2 :343.1693,found 343.1695。
Example 37
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -4,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -4; the desired product was obtained as (VIII) -4 in 87% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.02-7.96 (m, 2H), 7.94-7.86 (m, 2H), 7.56-7.50 (m, 1H), 7.42 (dt, j=18.7, 7.7hz, 5H), 7.22 (d, j=8.4 hz, 2H), 6.96-6.74 (m, 2H), 4.73 (t, j=7.4 hz, 1H), 3.74 (s, 3H), 3.16-2.85 (m, 2H), 2.56 (dd, j=14.0, 7.1hz, 1H), 2.27 (dt, j=14.0, 7.0hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.94,199.79,158.67,136.78,136.61,132.98,132.81,131.00,129.33,128.70,128.50,128.45,127.98,114.40,55.13,51.48,35.90,28.22.
Infrared spectrum (thin film, cm) -1 )3343,3060,3002,2955,2933,2836,1682,1608,1597,1581,1511,1449,1367,1303,1178,1111,1075,1034,11001,981,828,750,733,690,563,532。
High resolution mass spectrometry (APCI Source) calcd for C 24 H 23 O 3 :359.1642,found 359.1643。
Example 38
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -5,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -5; the desired product was obtained as (VIII) -5 in 95% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.03-7.94 (m, 2H), 7.95-7.84 (m, 2H), 7.59-7.50 (m, 1H), 7.50-7.46 (m, 1H), 7.45-7.36 (m, 4H), 7.28 (ddd, j=9.7, 5.9,3.2hz, 2H), 6.98 (t, j=8.6 hz, 2H), 4.80 (t, j=7.4 hz, 1H), 3.16-2.81 (m, 2H), 2.59 (dd, j=14.1, 7.1hz, 1H), 2.27 (dt, j=14.0, 6.9hz, 1H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 198.27,197.98,166.93 (d, j=17.3 Hz), 164.40 (d, j=17.6 Hz), 138.97,133.23 (d, j=3.0 Hz), 132.96 (d, j=2.9 Hz), 131.46 (d, j=9.3 Hz), 130.68 (d, j=9.3 Hz), 129.19,128.26,127.41,115.78 (d, j=2.3 Hz), 115.56 (d, j=2.2 Hz), 52.44,35.82,28.26; nuclear magnetic resonance fluorine spectrum (377 mhz, deuterated chloroform) delta-115.15.
Infrared spectrum (thin film, cm) -1 )3347,3064,2932,2857,1967,1898,1683,1597,1580,1507,1448,1417,1367,1277,1224,1179,1158,1098,1074,1001,979,960,832,752,731,690,556,516。
High resolution mass spectrometry (APCI Source) calcd for C 23 H 20 O 2 F:347.1442,found 347.1443。
Example 39
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -6,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -6; the desired product was obtained as (VIII) -6 in 99% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.02-7.95 (m, 2H), 7.94-7.87 (m, 2H), 7.51 (dd, j=15.3, 7.4hz, 2H), 7.41 (dt, j=10.5, 7.6hz, 4H), 7.35 (d, j=2.3 hz, 1H), 7.21 (d, j=3.8 hz, 3H), 4.80 (t, j=7.3 hz, 1H), 2.98 (qt, j=17.4, 6.8hz, 2H), 2.59 (dq, j=14.3, 7.1hz, 1H), 2.27 (dq, j=13.9, 6.9hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.56,198.98,141.08,136.63,136.27,134.73,133.15,133.08,130.19,128.68,128.58,128.53,128.28,127.92,127.46,126.53,51.75,35.72,28.19.
Infrared spectrum (thin film, cm) -1 )3345,3060,2959,2932,2872,1967,1812,1723,1683,1596,1580,1473,1448,1431,1367,1276,1222,1180,1124,1080,1001,980,884,842,783,755,718,689,595,569,548,491。
High resolution mass spectrometry (APCI Source) calcd for C 23 H 20 O 2 Cl:363.1146,found 363.1148。
Example 40
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in a formula (VII) -7,1, 5-dicarbonyl compound has a structure shown in a formula (VIII) -7; the desired product was obtained as (VIII) -7 in 99% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.97 (d, j=7.7 hz, 2H), 7.90 (d, j=7.8 hz, 2H), 7.58-7.46 (m, 2H), 7.40 (dt, j=12.7, 7.8hz, 6H), 7.20 (d, j=8.2 hz, 2H), 4.79 (t, j=7.4 hz, 1H), 2.97 (dt, j=10.2, 6.9hz, 2H), 2.59 (dd, j=14.1, 7.1hz, 1H), 2.34-2.19 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.54,199.13,138.07,136.60,136.25,133.08,133.05,132.05,129.97,128.63,128.53,128.50,127.89,121.18,51.52,35.66,28.03.
Infrared spectrum (thin film, cm) -1 )3346,3060,2959,2932,1967,1773,1683,1596,1580,1487,1448,1405,1367,1275,1222,1199,1178,1074,1011,1001,978,810,754,703,689,530。
High resolution mass spectrometry (APCI Source) calcd for C 23 H 20 O 2 Br:407.0641,found 407.0643。
Example 41
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -8,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -8; the desired product was obtained as (VIII) -8 in 97% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.92 (t, j=8.7 hz, 4H), 7.61-7.50 (m, 2H), 7.44 (q, j=8.2 hz, 4H), 5.04 (t, j=7.3 hz, 1H), 3.09 (t, j=6.8 hz, 2H), 2.78 (dq, j=14.0, 7.0hz, 1H), 2.30 (dq, j=14.0, 6.9hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 198.86,196.05,136.53,135.61,133.42,133.29,128.82,128.64,128.24,127.91,42.63,35.65,24.40; nuclear magnetic resonance fluorine spectrum (377 megahertz, deuterated chloroform) delta-140.83-
-140.98(m),-154.31(t,J＝20.9Hz),-160.87(td,J＝22.1,7.9Hz)。
Infrared spectrum (thin film, cm) -1 )3359,3062,2936,2641,2422,1967,1688,1655,1597,1581,1522,1501,1149,1273,1221,1182,1124,1001,970,948,864,847,723,700,661。
High resolution mass spectrometry (APCI Source) calcd for C 23 H 16 O 2 F 5 :419.1065,found 419.1064。
Example 42
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in a formula (VII) -9,1,5-dicarbonyl compound has a structure shown in a formula (VIII) -9; the desired product was obtained as (VIII) -9 in 99% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.06-7.96 (m, 2H), 7.94-7.88 (m, 2H), 7.61-7.51 (m, 4H), 7.43 (ddd, j=17.7, 8.9,6.6hz, 6H), 4.91 (t, j=7.3 hz, 1H), 2.99 (q, j=6.9 hz, 2H), 2.63 (dq, j=14.2, 7.1hz, 1H), 2.29 (dq, j=13.8, 6.8hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.53,199.01,143.19,136.65,136.28,133.30,133.18,129.67,129.34,128.71,128.59,127.95,125.94 (q, j=3.8 Hz), 123.98 (d, j= 272.0 Hz), 51.92,35.69,28.21.
Infrared spectrum (thin film, cm) -1 )3349,3062,2934,1922,1811,1683,1617,1597,1581,1449,1419,1367,1325,1277,11223,1166,1124,1069,1017,1001,977,831,752,728,699,666,610,569,528。
High resolutionMass spectrometry (APCI Source) calcd for C 24 H 20 O 2 F 3 :397.1410,found 397.1411。
Example 43
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -10,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -10; the desired product was obtained in 99% yield as (VIII) -10.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.98 (d, j=7.6 hz, 2H), 7.90 (d, j=7.5 hz, 2H), 7.58-7.45 (m, 2H), 7.41 (dt, j=14.8, 7.5hz, 4H), 7.33 (d, j=8.2 hz, 2H), 7.03 (d, j=8.3 hz, 2H), 4.82 (t, j=7.4 hz, 1H), 3.08-2.87 (m, 2H), 2.58 (dd, j=14.1, 7.1hz, 1H), 2.34-2.19 (m, 4H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.85,199.57,169.32,149.82,136.77,136.59,136.52,133.14,129.34,128.80,128.64,128.62,128.05,122.11,51.57,35.89,28.40,21.15.
Infrared spectrum (thin film, cm) -1 )3341,3085,3060,3036,2928,2872,2360,2341,1756,1677,1596,1580,1504,1447,1367,1275,1195,1166,1001,977,959,911,836,751,688,553。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 22 O 4 :386.1518,found 386.1514。
Example 44
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -11,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -11; the reaction time was 5h, and the desired product was obtained in 99% yield as (VIII) -11.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.07-8.00 (m, 2H), 7.95-7.88 (m, 2H), 7.85-7.72 (m, 4H), 7.58-7.32 (m, 9H), 4.98 (t, j=7.3 hz, 1H), 3.02 (qt, j=17.3, 6.9hz, 2H), 2.71 (dt, j=14.1, 7.1hz, 1H), 2.43 (dt, j=14.0, 6.9hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.95,199.63,136.89,136.73,136.71,133.68,133.07,132.99,132.60,128.95,128.84,128.58,128.06,127.81,127.67,127.32,126.28,125.97,52.59,36.00,28.35.
Infrared spectrum (thin film, cm) -1 )3342,3056,2931,2872,2360,2341,1677,1596,1579,1507,1447,1364,1275,1262,1195,1180,978,861,815,749,722,687,478。
High resolution mass spectrometry (APCI Source) calcd for C 27 H 22 O 2 :378.1620,found 378.1613。
Example 45
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -12,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -12; the reaction time was 5h, and the desired product was obtained as (VIII) -12 in 88% yield.
Hydrogen nuclear magnetic resonance (400 mhz, deuterated chloroform) delta 7.85-7.79 (m, 2H), 7.55-7.48 (m, 3H), 7.42-7.35 (m, 7H), 7.30 (s, 1H), 7.27-7.20 (m, 2H), 2.84 (ddd, j=14.5, 9.8,6.0hz, 2H), 2.49 (dt, j=10.1, 5.8hz, 2H), 1.67 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 203.06,199.90,143.67,136.64,136.28,132.92,131.88,129.59,129.06,128.48,128.06,128.04,127.11,126.22,54.15,34.74,34.08,24.33.
Infrared spectrum (thin film, cm) -1 )3337,3059,1025,2974,1934,1967,1679,1597,1580,1496,1447,1366,1317,1281,1244,1180,1077,1029,1002,166,846,761,742,715,702,690,572。
High resolution mass spectrometry (ESI source) calcd for C 24 H 22 O 2 Na + :365.1512,found 365.1515。
Example 46
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -13,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -13; the reaction time was 20h, and the desired product was obtained in 99% yield as (VIII) -13.
Hydrogen nuclear magnetic resonance (400 mhz, deuterated chloroform) delta 7.87-7.77 (m, 2H), 7.57-7.46 (m, 3H), 7.46-7.33 (m, 3H), 7.32-7.16 (m, 6H), 2.98-2.67 (m, 2H), 2.56-2.39 (m, 5H), 1.64 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 203.00,199.86,140.43,137.45,136.72,136.32,132.99,131.98,129.62,128.54,128.17,128.09,126.98,126.78,53.82,34.75,34.11,24.37,15.61.
Infrared spectrum (thin film, cm) -1 )3338,3058,2979,2921,2360,2341,1902,1673,1596,1578,1559,1492,1446,1365,1276,1240,1179,1100,965,822,748,689,659,571。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 24 O 2 S:388.1497,found 388.1491。
Example 47
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -14,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -14; the reaction time was 20h, and the desired product was obtained as (VIII) -14 in 85% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) δ 7.94-7.77 (m, 2H), 7.61-7.47 (m, 3H), 7.47-7.36 (m, 5H), 7.34-7.19 (m, 4H), 6.63 (s, 1H), 2.84 (ddd, j=13.4, 8.9,6.9hz, 2H), 2.47 (ddd, j=9.3, 6.6,2.0hz, 2H), 1.65 (s, 3H), 1.54 (s, 9H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 203.26,200.02,152.73,137.97,137.50,136.71,136.42,132.97,131.90,129.62,128.53,128.13,128.10,126.92,118.92,80.69,53.69,34.78,34.14,28.35,24.30.
Infrared spectrum (thin film, cm) -1 )3340,2977,2931,2361,2341,2294,1723,1672,1594,121,1448,1407,1366,1261,12333,1155,1052,977,906,838,765,749,737,689,574。
High resolution mass spectrometry (APCI Source) calcd for C 29 H 31 NO 4 :457.2253,found 457.2242。
Example 48
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -15,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -15; the reaction time was 2.5h, and the desired product was obtained as (VIII) -15 in 88% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.77-7.72 (m, 2H), 7.59 (d, j=7.8 hz, 2H), 7.52-7.44 (m, 1H), 7.42 (d, j=7.8 hz, 4H), 7.38-7.28 (m, 7H), 7.24 (t, j=7.3 hz, 2H), 7.17 (t, j=7.7 hz, 2H), 2.89-2.81 (m, 2H), 2.76 (dt, j=10.4, 4.1hz, 2H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 201.29,199.91,141.39,137.22,136.78,132.81,131.68,129.90,129.20,128.45,128.39,127.96,127.78,127.06,64.12,36.00,35.20.
Infrared spectrum (thin film, cm) -1 )3337,3058,3032,2979,1967,1683,1597,1580,1495,147,1364,1281,1224,1180,1377,1094,1001,990,968,845,753,701,653,587。
High resolution mass spectrometry (APCI Source) calcd for C 29 H 25 O 2 :405.1849,found 405.1852。
Example 49
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -16,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -16; the reaction time was 24h, and the desired product was obtained as (VIII) -16 in 79% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.84-7.76 (m, 2H), 7.62-7.56 (m, 2H), 7.52 (d, j=7.4 hz, 1H), 7.46-7.37 (m, 3H), 7.37-7.30 (m, 4H), 7.29-7.23 (m, 3H), 3.14 (ddd, j=16.0, 11.8,4.2hz, 1H), 2.62 (ddd, j=16.0, 11.8,4.2hz, 1H), 2.49 (ddd, j=13.6, 11.8,4.2hz, 1H), 2.20 (ddd, j=13.5, 11.8,4.2hz, 1H), 1.69 (ddd, j=8.6, 5.7,2.8hz, 1H), 0.76-0.65 (m, 1H), 0.31.0-0 (m, 0.04); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 201.79,199.94,141.29,136.76,136.36,132.92,131.96,130.02,128.50,128.47,128.17,128.05,128.02,127.25,57.33,34.17,30.85,18.03,3.87,0.15.
Infrared spectrum (thin film, cm) -1 )3060,3023,2924,2853,2361,2341,1676,1597,1579,1493,1447,1277,1237,1179,1002,972,846,790,751,704,690,581。
High resolution mass spectrometry (APCI Source) calcd for C 26 H 24 O 2 :368.1776,found 368.1768。
Example 50
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -17,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -17; the reaction time was 20h, and the desired product was obtained as (VIII) -17 in 83% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) δ 7.78 (dd, j=8.4, 1.4hz, 2H), 7.73-7.67 (m, 2H), 7.58 (dd, j=8.4, 1.3hz, 2H), 7.51 (t, j=7.4 hz, 1H), 7.46-7.31 (m, 6H), 7.25 (dd, j=8.4, 7.1hz, 2H), 3.15 (ddd, j=14.5, 9.1,6.1hz, 1H), 2.96-2.68 (m, 3H), 1.99 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 198.98,196.24,169.17,137.34,136.75,135.29,132.96,132.15,129.11,128.91,128.52,128.37,128.08,128.01,125.04,88.50,32.54,31.81,21.17.
Infrared spectrum (thin film, cm) -1 )3351,3087,3059,3027,2959,2845,2360,2341,1740,1680,1492,1447,1368,1255,1216,1182,1101,1002,881,848,748,699,689,660,635,606,578,522。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 22 O 4 :386.1518,found 386.1508。
Example 51
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure of formulas (E) - (VII) -18 (E configuration), and the 1, 5-dicarbonyl compound has a structure of formulas (VIII) -18; the reaction time was 2.5h, and the obtained target product was (viii) -18 in 80% yield, mainly diastereoisomers, d.r. value 9.0:1.
nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.14-7.11 (m, 15H), 4.61 (d, j=9.5 hz, 1H), 3.27 (dd, j=15.1, 3.7hz, 1H), 3.10 (dtt, j=9.8, 6.4,3.3hz, 1H), 2.74 (dd, j=15.1, 9.2hz, 1H), 0.83 (d, j=6.8 hz, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.97,199.82,137.45,137.08,136.94,132.97,128.99,128.82,128.62,128.55,128.42,128.33,127.98,127.29,59.06,44.34,33.54,17.39.
Infrared spectrum (thin film, cm) -1 )3337,3060,3057,2965,29331966,1680,1597,1580,1492,1517,1363,1278,1214,1179,1074,1001,94,894,837,751,698,658,526。
High resolution mass spectrometry (APCI Source) calcd for C 24 H 23 O 2 :343.1693,found 343.1692。
Example 52
This embodiment is substantially the same as embodiment 51 except that:
the olefin compound has a structure of formula (Z) - (VII) -18 (Z configuration); the yield of the desired product (viii) -18 was 83%, mainly diastereoisomers, d.r. value 3.5:1.
example 53
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -19,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -19; the reaction time was 10h, and the desired product was obtained as (VIII) -19 in 70% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.08-7.99 (m, 2H), 7.96-7.85 (m, 2H), 7.61-7.16 (m, 11H), 5.40 (s, 1H), 3.26 (d, j=17.3 hz, 1H), 2.98 (d, j=17.3 hz, 1H), 0.81-0.53 (m, 3H), 0.50-0.33 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.78,199.72,137.50,137.36,137.05,133.07,132.88,129.84,128.89,128.72,128.58,128.55,128.01,127.37,54.84,45.33,18.72,9.18,8.30.
Infrared spectrum (thin film, cm) -1 )3350,3061,3005,2924,2361,2341,1680,1596,1580,1447,1358,1274,1208,1179,1077,1023,978,833,751,689,652,599,513。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 22 O 2 :354.1620,found 354.1612。
Example 54
This embodiment is substantially the same as embodiment 34 except that:
The olefin compound has a structure shown in the formula (VII) -20,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -20; the reaction time was 10 hours, and the objective product was obtained as (VIII) -20 in a yield of 60%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.10-7.99 (m, 2H), 7.91 (d, j=7.5 hz, 2H), 7.54 (t, j=7.4 hz, 1H), 7.49 (t, j=7.3 hz, 1H), 7.40 (ddd, j=22.0, 10.7,7.2hz, 6H), 7.30 (t, j=7.3 hz, 2H), 7.26 (d, j=7.0 hz, 1H), 5.40 (s, 1H), 3.26 (d, j=17.2 hz, 1H), 2.99 (d, j=17.3 hz, 1H), 0.68 (t, j=6.2 hz, 1H), 0.64-0.57 (m, 2H), 0.50-0.35 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.70,199.64,137.52,137.38,137.01,132.96,132.78,129.78,128.80,128.50,128.47,127.95,127.30,54.84,45.22,18.73,9.16,8.28.
Infrared spectrum (thin film, cm) -1 )3060,3005,2918,236,2341,1680,1596,1580,1596,1580,1491,1447,1358,1266,1208,1178,1001,833,797,751,733,688,651,599,512。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 22 O 2 :354.1620,found 354.1612。
Example 55
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -21,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -21; the reaction time was 10 hours, and the objective product was obtained as (VIII) -21 in a yield of 81%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) δ 7.86-7.80 (m, 2H), 7.62 (dd, j=8.2, 1.4hz, 2H), 7.59-7.55 (m, 1H), 7.50 (d, j=7.4 hz, 1H), 7.38 (td, j=10.0, 8.9,6.9hz, 4H), 7.29-7.21 (m, 4H), 6.74 (s, 1H), 3.04 (ddd, j=16.1, 10.8,5.0hz, 1H), 2.87 (ddd, j=16.4, 10.7,5.4hz, 1H), 2.75-2.51 (m, 2H), 1.75 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 200.21,199.41,159.97,154.66,136.73,136.57,133.00,132.20,128.75,128.54,128.34,128.28,128.08,124.19,123.00,120.94,111.40,103.06,51.51,33.90,32.76,23.12.
Infrared spectrum (thin film, cm) -1 )3085,3060,2981,2933,2360,2341,1679,1596,1578,1449,1365,1251,1239,1212,1169,965,941,883,750,738,689,570。
High resolution mass spectrometry (APCI Source) calcd for C 26 H 22 O 3 :382.1569,found 382.1564。
Example 56
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -22,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -22; the reaction time was 20h, and the desired product was obtained as (VIII) -22 in 91% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.86-7.76 (m, 2H), 7.55-7.48 (m, 3H), 7.40 (t, j=7.6 hz, 3H), 7.33 (dd, j=5.0, 2.9hz, 1H), 7.26 (t, j=7.8 hz, 2H), 7.21 (dd, j=3.0, 1.4hz, 1H), 6.96 (dd, j=5.0, 1.4hz, 1H), 2.85 (ddd, j=26.6, 10.2,5.9hz, 2H), 2.50 (ddd, j=10.3, 7.3,5.5hz, 2H), 1.66 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 202.97,199.81,144.99,136.85,136.74,132.99,131.90,129.20,128.55,128.16,128.09,126.76,126.64,120.46,52.14,34.48,34.10,24.57.
Infrared spectrum (thin film, cm) -1 )3062,3025,2974,2931,2360,2341,1673,1596,1579,1447,1365,1280,1242,1211,1179,977,929,749,714,689,666。
High resolution mass spectrometry (APCI Source) calcd for C 22 H 20 O 2 S:348.1184,found 348.1182。
Example 57
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -23,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -23; the reaction time was 10h, and the desired product was obtained as (VIII) -23 in 70% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.03-7.95 (m, 2H), 7.95-7.86 (m, 2H), 7.60-7.49 (m, 2H), 7.44 (dt, j=15.5, 7.6hz, 4H), 3.60 (dtd, j=8.6, 6.5,4.8hz, 1H), 3.17-2.98 (m, 1H), 2.85 (ddd, j=17.1, 8.3,6.6hz, 1H), 2.34-2.14 (m, 1H), 2.14-1.96 (m, 1H), 1.86-1.73 (m, 1H), 1.53 (dd, j=14.6, 6.7hz, 1H), 1.29 (dq, j=7.3, 3.9,3.2hz, 4H), 0.85 (q, j=5.6 hz, 3.6 hz). Nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 204.04,199.92,137.26,136.79,133.02,132.99,128.69,128.53,128.24,128.00,45.12,35.91,32.27,29.51,26.09,22.81,13.87.
Infrared spectrum (thin film, cm) -1 )3350,3061,2956,2930,2858,173,1683,1597,1580,1448,1345,1270,1224,1180,1124,1074,1001,972,752,705,689。
High resolution mass spectrometry (APCI Source) calcd for C 21 H 25 O 2 :309.1849,found 309.1851。
Example 58
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -24,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -24; the reaction time was 20h, and the desired product was obtained as (VIII) -24 in a yield of 51%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) δ 7.97 (d, j=7.7 hz, 2H), 7.90 (d, j=7.7 hz, 2H), 7.54 (d, j=9.3 hz, 2H), 7.47-7.33 (m, 4H), 3.60 (t, j=6.7 hz, 1H), 3.05 (dd, j=16.3, 8.0hz, 1H), 2.92-2.77 (m, 1H), 2.31-2 (m, 1H), 2.02 (dd, j=13.8, 6.9hz, 1H), 1.80 (dd, j=14.1, 7.2hz, 1H), 1.51 (dt, j=13.8, 6.7hz, 1H), 1.23 (d, j=13.0 hz, 24H), 0.88 (d, j=6.4 hz, 3H). Nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 204.09,199.97,137.28,136.81,133.05,133.03,128.72,128.57,128.28,128.04,45.19,35.96,32.60,31.94,29.77,29.70,29.66,29.63,29.57,29.43,29.38,27.38,26.10,22.71,14.14.
Infrared lightSpectrum (thin film, cm) -1 )2922,2852,2360,2341,1680,1597,1580,1448,1275,1261,1220,972,763,689。
High resolution mass spectrometry (APCI Source) calcd for C 31 H 44 O 2 :448.3341,found 448.3340.
Example 59
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -25,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -25; the reaction time was 10h, and the desired product was obtained as (VIII) -25 in 93% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.88 (dd, j=8.3, 1.4hz, 2H), 7.81-7.67 (m, 2H), 7.57-7.50 (m, 1H), 7.47 (d, j=7.4 hz, 1H), 7.45-7.36 (m, 4H), 2.90 (td, j=10.4, 5.4hz, 2H), 2.38 (ddd, j=14.3, 10.8,5.4hz, 1H), 2.15-1.91 (m, 2H), 1.74 (dd, j=14.3, 7.3hz, 1H), 1.32 (s, 3H), 0.87 (t, j=7.5 hz, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 208.28,199.85,139.16,136.72,133.08,131.22,128.59,128.35,128.08,127.56,51.31,33.99,33.37,32.41,22.34,8.88.
Infrared spectrum (thin film, cm) -1 )3060,2968,2933,2361,2341,1672,1597,1579,1447,1366,1277,1213,1178,1002,970,744,717,689,655,568。
High resolution mass spectrometry (APCI Source) calcd for C 20 H 22 O 2 :294.1620,found 294.1613。
Example 60
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -26,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -26; the reaction time was 20h, and the desired product was obtained as (VIII) -26 in 85% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.93 (ddd, j=8.5, 6.2,1.8hz, 4H), 7.44 (ddt, j=36.3, 15.5,7.3hz, 6H), 3.84-3.60 (m, 2H), 3.21-2.95 (m, 2H), 2.48 (t, j=7.5 hz, 2H), 2.28-2.01 (m, 4H), 1.61 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.78,198.32,175.29,136.61,135.78,133.14,132.11,128.58,128.29,128.16,127.87,65.16,44.21,33.83,31.28,31.12,22.36,18.76.
Infrared spectrum (thin film, cm) -1 )3350,2983,2920,2360,2341,1675,1596,1579,1447,1411,1276,1261,1179,1147,969,745,707,690,583,483。
High resolution mass spectrometry (APCI Source) calcd for C 22 H 23 NO 3 :349.1678,found 349.1476。
Example 61
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -27,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -27; the reaction time was 10h, and the desired product was obtained as (VIII) -27 in 70% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.10-7.84 (m, 2H), 7.82-7.70 (m, 2H), 7.67-7.48 (m, 2H), 7.44 (td, j=7.6, 1.5hz, 4H), 7.40-7.30 (m, 5H), 5 (s, 2H), 3.91 (s, 2H), 3.25-2.81 (m, 4H), 2.57-2.29 (m, 4H), 1.62 (s, 2H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 206.71,198.95,155.27,138.42,136.78,136.53,133.30,131.84,128.65,128.58,128.51,128.01,127.88,127.72,67.10,50.14,41.12,34.03,32.96.
Infrared spectrum (thin film, cm) -1 )3058,2923,2872,2360,2341,2278,1684,1597,1430,1360,1277,1215,1146,1092,961,733,692,456。
High resolution mass spectrometry (APCI Source) calcd for C 29 H 29 NO 4 :455.2097,found 455.2095。
Example 62
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -28,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -28; the reaction time was 10h, and the desired product was obtained as (VIII) -28 in 60% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.91 (dd, j=8.3, 1.4hz, 2H), 7.80 (dd, j=8.3, 1.4hz, 2H), 7.57-7.52 (m, 1H), 7.46 (dt, j=21.2, 7.5hz, 3H), 7.35 (t, j=7.8 hz, 2H), 3.71 (dt, j=8.3, 4.3hz, 1H), 3.09 (dd, j=16.9, 8.5hz, 1H), 2.93 (dd, j=16.9, 5.1hz, 1H), 2.73 (dd, j=7.3, 3.9hz, 1H), 1.92 (ddd, j=14.4, 7.3.8 hz, 2H), 1.76 (dd, j=7.5, 3.8hz, 1.1H), 1.63 (dd, 1.9 hz, 1H), 2.73 (dd, 1.9 hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 203.60,199.76,137.06,136.79,132.94,132.88,128.71,128.49,128.23,128.05,46.50,38.76,33.57,29.25,25.74,23.71,22.79.
Infrared spectrum (thin film, cm) -1 )3337,3059,29930,2856,1680,1597,1580,1448,1370,1324,1280,1253,1214,1178,1010,981,946,854,752,700,691,662,567。
High resolution mass spectrometry (APCI Source) calcd for C 21 H 23 O 2 :307.1693,found 307.1695。
Example 63
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -29,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -29; the reaction time was 10h, and the desired product was obtained in the form of (VIII) -29 with a yield of 70%.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.12-7.98 (m, 2H), 7.98-7.85 (m, 2H), 7.69-7.51 (m, 2H), 7.51-7.37 (m, 4H), 5.94 (ddd, j=17.1, 10.3,8.7hz, 1H), 5.34-5.09 (m, 2H), 4.25 (td, j=8.4, 6.6hz, 1H), 3.37-3.06 (m, 1H), 2.99 (ddd, j=17.4, 7.2,6.0hz, 1H), 2.37 (dd, j=13.9, 6.8hz, 1H), 2.12-1.97 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 200.64,199.75,136.91,136.48,133.16,133.09,129.26,128.64,128.61,128.19,128.02,118.53,50.58,35.51,26.19.
Infrared spectrum (thin film, cm) -1 )3060,2922,2852,2360,2341,1678,1634,1596,1579,1447,1364,1276,1278,1179,992,924,751,699,568。
High resolution mass spectrometry (APCI Source) calcd for C 19 H 18 O 2 :278.1307,found 278.1298。
Example 64
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -30,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -30; the reaction time was 10h, and the desired product was obtained in the form of (VIII) -30 in 80% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.08-7.96 (m, 2H), 7.88-7.79 (m, 2H), 7.58-7.47 (m, 2H), 7.47-7.29 (m, 4H), 5.14 (dt, j=5.2, 1.1hz, 2H), 2.94-2.72 (m, 2H), 2.32 (dddd, j=47.6, 14.2,11.0,5.2hz, 2H), 1.78 (s, 3H), 1.42 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 203.44,200.01,148.00,136.94,136.83,132.97,132.33,128.96,128.56,128.26,128.07,112.62,55.67,33.92,31.63,22.76,20.67.
Infrared spectrum (thin film, cm) -1 )34743061,2972,2923,2854,2361,2341,1675,1636,1597,1579,1447,1380,1277,1260,1237,1209,1179,966,896,747,689,578。
High resolution mass spectrometry (APCI Source) calcd for C 21 H 22 O 2 :306.1620,found 306.1613。
Example 65
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -31,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -31; the reaction time was 15h and the desired product was obtained as (VIII) -31 in 84% yield, predominantly diastereoisomer, d.r. value 1.3:1.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.91-7.85 (m, 2H), 7.84-7.80 (m, 2H), 7.57-7.47 (m, 2H), 7.44-7.38 (m, 4H), 5.38 (dt, j=5.5, 1.9hz, 1H), 3.01-2.83 (m, 2H), 2.51-2.25 (m, 2H), 2.23-1.83 (m, 5H), 1.62 (d, j=2.2 hz, 3H), 1.53-1.32 (m, 2H), 1.24 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 208.78,199.87 (d, j=7.6 Hz), 139.49,136.70,134.10,133.10,131.16,128.58,128.37,128.08,127.59,120.41,54.09,40.59,33.98,31.14,26.24,25.26,23.32,18.19.
Infrared spectrum (thin film, cm) -1 )3057,2927,2360,2341,1679,1597,1449,1379,1277,1260,1212,1179,976,958,746,689,591,567,430,413。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 28 O 2 :360.2089,found 360.2085。
Example 66
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -32,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -32; the reaction time was 10h, and the desired product was obtained as (VIII) -32 in 87% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 7.77-7.70 (m, 2H), 7.58-7.46 (m, 3H), 7.39-7.17 (m, 11H), 6.81 (d, j=8.8 hz, 2H), 5.04 (p, j=6.3 hz, 1H), 2.90-2.65 (m, 4H), 1.59 (s, 6H), 1.14 (t, j=6.9 hz, 6H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 201.03,199.67,173.49,154.70,140.39,137.11,136.72,133.88,132.99,132.95,131.86,130.62,129.82,128.56,128.50,127.98,127.93,118.55,79.12,68.99,63.11,35.73,35.08,25.44,25.32,21.55,21.51.
Infrared spectrum (thin film, cm) -1 )3059,298,2933,2360,2341,1906,1727,1677,1597,1579,1507,1491,1447,13117,1280,1246,1178,1149,1100,1002,972,930,820,744,691,585。
High resolution mass spectrometry (APCI Source) calcd for C 36 H 35 ClO 5 :582.2173,found 582.2168。
Example 67
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -33,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -33; the reaction time was 10h and the desired product was obtained as (VIII) -33 in 97% yield, predominantly diastereoisomer, d.r. value 1.2:1.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) δ 7.79-7.73 (m, 2H), 7.57 (d, j=7.8 hz, 2H), 7.53-7.40 (m, 3H), 7.39-7.23 (m, 9H), 7.24-7.12 (m, 3H), 3.66 (q, j=7.0 hz, 1H), 3.55 (s, 3H), 2.90-2.70 (m, 4H), 1.41 (d, j=7.2 hz, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 201.25,199.89,174.68,141.76,141.29,140.72,140.62,137.31,136.89,132.86,131.68,129.95,129.22,129.02,128.77,128.55,128.45,128.02,127.80,127.21,126.06,64.32,51.95,45.46,45.36,35.22,18.50.
Infrared spectrum (thin film, cm) -1 )3057,2982,2937,2360,2341,1733,1676,1597,1580,1489,1434,1263,1222,1168,1068,969,750,734,700,572。
High resolution mass spectrometry (APCI Source) calcd for C 33 H 30 O 4 :490.2144,found 490.2140。
Example 68
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -34,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -34; the reaction time was 20h and the desired product was obtained as (VIII) -34 in a yield of 90%, mainly diastereoisomers, d.r. value 3.0:1.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.89 (d, j=7.6 hz, 2H), 7.79 (d, j=7.2 hz, 2H), 7.57-7.35 (m, 6H), 7.18 (d, j=8.0 hz, 2H), 7.08 (d, j=7.9 hz, 2H), 3.71-3.62 (m, 4H), 3.08-2.83 (m, 2H), 2.70-
2.50 (m, 3H), 2.40 (t, j=12.5 hz, 1H), 2.25-2.04 (m, 1H), 1.71 (dddd, j=68.5, 12.4,9.6,6.6hz, 4H), 1.47 (dd, j=7.2, 2.0hz, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 206.86,199.91,175.14,140.10,138.12,137.91,136.69,133.13,131.49,129.14,128.61,128.38,128.10,128.01,127.43,61.11,52.02,48.81,45.01,35.85,35.08,29.93,27.94,22.43,18.61.
Infrared spectrum (thin film, cm) -1 )3056,2949,2874,2360,2341,1734,1669,1596,1579,1512,1435,1260,1207,1165,1066,1001,970,859,748,690,567,538。
High resolution mass spectrometry (APCI Source) calcd for C 31 H 32 O 4 :468.2301,found 468.2236。
Example 69
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -35,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -35; the reaction time was 10h, and the desired product was obtained in the form of (VIII) -35 in 99% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 7.85-7.73 (m, 2H), 7.60-7.54 (m, 2H), 7.54-7.46 (m, 1H), 7.41-7.33 (m, 4H), 7.20 (dd, j=8.3, 7.4hz, 2H), 7.10 (d, j=1.7 hz, 1H), 2.83 (ddd, j=9.6, 5.9,4.8hz, 2H), 2.63-2.42 (m, 4H), 1.76-1.64 (m, 5H), 1.38 (s, 9H), 1.11 (d, j=16.9 hz, 6H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 203.57,200.16,154.09,150.56,139.14,137.86,136.79,136.38,132.90,132.10,129.19,128.51,128.06,128.00,120.57,117.61,54.39,43.15,41.39,34.96,33.99,32.79,31.71,29.28,28.39,23.94.
Infrared spectrum (thin film, cm) -1 )3086,3062,2953,2862,2360,2341,1676,1597,1589,1447,1361,1277,1259,1236,1179,976,953,749,716,689,605。
High resolution mass spectrometry (APCI Source) calcd for C 31 H 38 O 2 :466.2872,found 466.2866。
Example 70
This embodiment is substantially the same as embodiment 34 except that:
the olefin compound has a structure shown in the formula (VII) -36,1,5-dicarbonyl compound has a structure shown in the formula (VIII) -36; the reaction time was 48h, and the desired product was obtained as (VIII) -36 in 55% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.85 (d, j=8.0 hz, 2H), 7.62 (d, j=7.7 hz, 2H), 7.55-7.29 (m, 6H), 4.02 (d, j=7.8 hz, 1H), 2.79-2.46 (m, 3H), 2.17-1.09 (m, 23H), 1.00 (s, 3H), 0.84-0.71 (m, 4H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 208.27,200.03,140.71,136.54,133.01,131.41,128.51,128.49,128.29,127.96,66.50,66.08,53.56,51.26,48.19,39.04,36.89,36.05,35.85,35.19,34.56,32.09,31.99,30.79,28.96,28.51,25.17,20.92,16.73,16.34,11.17.
Infrared spectrum (thin film, cm) -1 )3368,2921,2853,2360,2341,1681,1660,1597,1447,1262,1210,1178,1009,966,748,691。
High resolution mass spectrometry (APCI Source) calcd for C 35 H 44 O 3 :512.3290,found 512.3280。
Example 71
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -2, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -37; the reaction time was 2.5h, and the desired product was obtained in 99% yield as (VIII) -37.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.04-7.94 (m, 2H), 7.94-7.84 (m, 2H), 7.34-7.25 (m, 4H), 7.23-7.16 (m, 1H), 6.94-6.81 (m, 4H), 4.72 (t, j=7.3 hz, 1H), 3.82 (d, j=16.9 hz, 6H), 3.04-2.93 (m, 1H), 2.86 (dt, j=16.7, 6.7hz, 1H), 2.58 (dt, j=14.0, 7.2hz, 1H), 2.25 (dt, j=13.9, 6.9hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 198.53,198.13,163.36,163.28,139.65,131.03,130.28,129.92,129.64,128.90,128.22,127.02,113.64,113.62,55.38,55.34,52.10,35.71,28.61.
Infrared spectrum (thin film, cm) -1 )3061,2962,2935,2839,1671,1600,1574,1510,1454,1419,1363,1313,1259,1163,1114,1029,982,837,752,702。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 25 O 4 :389.1747,found 389.1750。
Example 72
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -3, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -38; the reaction time was 2.5h, and the desired product was obtained as (VIII) -38 in 97% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) δ 7.89 (d, j=8.2 hz, 2H), 7.81 (d, j=8.1 hz, 2H), 7.35-7.27 (m, 4H), 7.24-7.15 (m, 5H), 4.76 (t, j=7.3 hz, 1H), 3.05-2.82 (m, 2H), 2.59 (dt, j=14.1, 7.2hz, 1H), 2.39 (s, 3H), 2.34 (s, 3H), 2.32-2.22 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.56,199.21,143.72,143.66,139.41,134.35,134.13,129.18,129.16,128.93,128.87,128.27,128.12,127.07,52.29,35.89,28.38,21.56,21.52.
Infrared spectrum (thin film, cm) -1 )3337,3060,3029,2925,1923,1679,1606,1572,1492,1453,1408,1365,
1277,1227,1179,1119,1072,102,977,842,790,750,701,566,519。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 25 O 2 :357.1849,found 357.1852。
Example 73
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -4, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -39; the reaction time was 2.5h, and the desired product was obtained as (VIII) -39 in 80% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.92 (d, j=8.4 hz, 2H), 7.85 (d, j=8.4 hz, 2H), 7.42 (d, j=8.4 hz, 2H), 7.36 (d, j=8.6 hz, 2H), 7.32-7.22 (m, 5H), 4.71 (t, j=7.3 hz, 1H), 3.06-2.82 (m, 2H), 2.58 (dd, j=14.1, 7.1hz, 1H), 2.27 (dd, j=14.0, 6.9hz, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 198.58,198.27,139.53,139.39,138.72,135.04,134.80,130.17,129.42,129.18,128.88,128.83,128.21,127.43,52.44,35.79,28.06.
Infrared spectrum (thin film, cm) -1 )3350,3062,3028,2959,2933,1684,1588,1570,1489,1399,1366,1276,
1221,1175,1093,1013,984,827,766,748,700,569,533,517。
High resolution mass spectrometry (APCI Source) calcd for C 23 H 19 O 2 Cl 2 :397.0757,found 397.0760。
Example 74
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -5, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -40; the reaction time was 2.5h, and the desired product was obtained as (VIII) -40 in 92% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.02-7.92 (m, 2H), 7.92-7.82 (m, 2H), 7.25 (d, j=6.4 hz, 4H), 7.20-7.15 (m, 1H), 7.03 (dt, j=21.6, 8.7hz, 4H), 4.68 (t, j=7.3 hz, 1H), 3.05-2.77 (m, 2H), 2.53 (dq, j=14.3, 7.2hz, 1H), 2.23 (dt, j=13.9, 7.0hz, 1H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 198.27,197.98,166.93 (d, j=17.3 Hz), 164.40 (d, j=17.6 Hz), 138.97,133.23 (d, j=3.0 Hz), 132.96 (d, j=2.9 Hz), 131.46 (d, j=9.3 Hz), 130.68 (d, j=9.3 Hz), 129.19,128.26,127.41,115.78 (d, j=2.3 Hz), 115.56 (d, j=2.2 Hz), 52.44,35.82,28.26; nuclear magnetic resonance fluorine spectrum (377 mhz, deuterated chloroform) δ -105.15, -105.19.
Infrared spectrum (thin film, cm) -1 )3345,3064,3029,29331683,1597,1506,1454,1409,1367,1272,1230,1156,1099,1012,985,842,752,702,606,566,521。
High resolution mass spectrometry (APCI Source) calcd for C 23 H 19 O 2 F 2 :365.1348,found 365.1348。
Example 75
This embodiment is substantially the same as embodiment 34 except that:
The 1, 3-dicarbonyl compound is shown as a formula (VI) -6, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -41; the reaction time was 2.5h, and the desired product was obtained as (VIII) -41 in 89% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ8.04 (d, j=8.1 hz,2 h), 7.98 (d, j=8.0 hz,2 h), 7.68 (d, j=8.1 hz,2 h), 7.62 (d, j=8.1 hz,2 h), 7.27 (dq, j=15.4, 7.7hz,5 h), 4.74 (t, j=7.3 hz,1 h), 2.98 (q, j=7.0 hz,2 h), 2.58 (dq, j=14.2, 7.1hz,1 h), 2.30 (dt, j=14.0, 7.0hz,1 h); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 198.79,198.48,139.35,139.18,138.28,134.51 (d, j=25.0 Hz), 134.18 (d, j=25.2 Hz), 129.37,129.11,128.37,128.28,127.69 125.65 (q, j=3.7 Hz), 125.69 (q, j=3.7 Hz), 123.57 (d, j=272.7 Hz), 123.51 (d, j=272.7 Hz), 52.80,36.07,27.86; 19 nuclear magnetic resonance fluorine spectrum (377 mhz, deuterated chloroform) δ -63.14, -63.21.
Infrared spectrum (thin film, cm) -1 )3064,3029,2936,1689,1600,1582,1512,1454,1410,1326,1275,1221,1169,1130,1067,1016,987,856,833,746,725,600。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 19 O 2 F 6 :465.1284,found 465.1288。
Example 76
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -7, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -42; the reaction time was 2.5h, and the desired product was obtained as (VIII) -42 in 77% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ8.02 (d, j=8.1 hz,2 h), 7.98 (d, j=8.1 hz,2 h), 7.74 (d, j=8.1 hz,2 h), 7.67 (d, j=8.2 hz,2 h), 7.31 (t, j=7.1 hz,2 h), 7.24 (dd, j=9.8, 7.9hz,3 h), 4.71 (t, j=7.3 hz,1 h), 2.98 (td, j=6.8, 3.5hz,2 h), 2.57 (dd, j=14.1, 7.1hz,1 h), 2.29 (dd, j=14.1, 7.1hz,1 h); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 198.27,197.99,139.51,139.40,137.83,132.49,132.37,129.42,129.10,128.37,128.19,127.80,117.81,117.78,116.44,116.17,52.76,35.94,27.60.
Infrared spectrum (thin film, cm) -1 )3359,3062,2930,2230,1688,1606,1566,1491,1453,1404,1368,1312,1272,1219,1175,1113,1031,987,834,739,703,576,546。
High resolution mass spectrometry (APCI Source) calcd for C 25 H 19 O 2 N 2 :379.1441,found 379.1445。
Example 77
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -8, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -43; the reaction tube was placed at a distance of about 1cm from a 10W 400nm LED light source for a reaction time of 2.5h to give the desired product (VIII) -43 in 94% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.01-7.93 (m, 2H), 7.51-7.44 (m, 1H), 7.37 (dd, j=8.3, 6.8hz, 2H), 7.33-7.24 (m, 4H), 7.24-7.17 (m, 1H), 4.70-4.59 (m, 1H), 2.47-2.31 (m, 3H), 2.18-2.09 (m, 1H), 2.08 (s, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 208.38,199.47,138.96,136.57,132.89,128.98,128.68,128.48,128.24,127.19,52.18,40.91,29.92,27.60.
Infrared spectrum (thin film, cm) -1 )3084,3027,2961,2933,1714,1680,1597,1490,1368,1269,1176,1159,1072,756,699。
High resolution mass spectrometry (APCI Source) calcd for C 18 H 19 O 2 :267.1380,found 267.1382。
Example 78
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -9, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -44; the reaction tube was placed at a distance of about 1cm from a 10W 400nm LED light source for a reaction time of 2.5 hours to give the desired product (VIII) -44 in a yield of 95%.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.95 (dd, j=8.4, 1.4hz, 2H), 7.50-7.44 (m, 1H), 7.37 (dd, j=8.3, 6.9hz, 2H), 7.28 (d, j=5.6 hz, 4H), 7.20 (td, j=5.6, 3.1hz, 1H), 4.67 (dd, j=8.0, 6.0hz, 1H), 2.56-2.28 (m, 5H), 2.22-2.03 (m, 1H), 1.02 (t, j=7.3 hz, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 211.15,199.61,139.08,136.71,132.91,129.01,128.73,128.52,128.33,127.21,52.30,39.59,35.93,27.75,7.82.
Infrared spectrum (thin film, cm) -1 )3361,3184,3061,2972,2921,2851,2361,2341,1710,1678,1597,1492,1447,1371,1342,1262,1176,1160,1115,1073,982,955,832,756,666,570,517。
High resolution mass spectrometry (APCI Source) calcd for C 19 H 20 O 2 :280.1463,found 280.1458。
Example 79
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -10, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -45; the reaction tube was placed at a distance of about 1cm from a 10W 400nm LED light source for a reaction time of 2.5 hours to give the desired product (VIII) -45 in 87% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.02-7.88 (m, 2H), 7.49-7.42 (m, 1H), 7.37 (dd, j=8.4, 6.9hz, 2H), 7.28 (d, j=5.5 hz, 4H), 7.23-7.09 (m, 1H), 4.72-4.61 (m, 1H), 2.49-2.34 (m, 3H), 2.31 (t, j=7.3 hz, 2H), 2.11 (d, j=7.2 hz, 1H), 1.56 (q, j=7.4 hz, 2H), 0.87 (t, j=7.4 hz, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 210.74,199.63,139.08,136.73,132.91,129.00,128.73,128.52,128.33,127.21,52.28,44.77,40.00,27.71,17.28,13.72.
Infrared spectrum (thin film, cm) -1 )3360,3184,2960,2921,2851,2361,2341,1708,1678,1597,1447,1261,1159,1126,959,753,697,570,517。
High resolution mass spectrometry (APCI Source) calcd for C 20 H 22 O 2 :294.1620,found 294.1611。
Example 80
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -11, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -46; the reaction tube was placed at a distance of about 1cm from a 10W 400nm LED light source for a reaction time of 2.5 hours to give the desired product (VIII) -45 in 91% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.05-7.88 (m, 2H), 7.52-7.43 (m, 1H), 7.37 (ddd, j=8.2, 6.7,1.4hz, 2H), 7.28 (d, j=5.0 hz, 4H), 7.20 (ddd, j=6.5, 4.7,3.4hz, 1H), 4.69 (t, j=7.2 hz, 1H), 2.73-2.30 (m, 4H), 2.12 (dd, j=7.0, 5.6hz, 1H), 1.03 (dd, j=7.0, 6.0hz, 6H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 214.41,199.72,139.09,136.76,132.90,128.97,128.73,128.52,128.36,127.19,52.19,40.83,37.55,27.70,18.29,18.23.
Infrared spectrum (thin film, cm) -1 )3360,3184,2964,2921,2851,2361,2340,1707,1678,1597,1468,1447,1324,1274,1176,1073,1011,957,753,697,582,515。
High resolution mass spectrometry (APCI Source) calcd for C 20 H 22 O 2 :294.1620,found 194.1613。
Example 81
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -12, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -47; the reaction time was 2.5h, and the desired product was obtained as (VIII) -47 in 93% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) δ 7.87 (d, j=7.7 hz, 2H), 7.38 (t, j=7.9 hz, 3H), 7.32-7.18 (m, 9H), 7 (dq, j=6.2, 2.7hz, 1H), 7.01 (t, j=7.4 hz, 1H), 4.69 (t, j=7.2 hz, 1H), 2.53-2.41 (m, 1H), 2.31-2.15 (m, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 198.71,169.69,137.85,136.80,135.47,132.02,128.05,127.95,127.77,127.53,127.32,126.28,123.22,118.84,51.34,33.87,28.31.
Infrared spectrum (thin film, cm) -1 )3084,3027,2961,2933,1713,1680,1597,1580,1490,1369,1269,1176,1160,1072,1001,756,699。
High resolution mass spectrometry (APCI Source) calcd for C 23 H 21 NO 2 :343.1572,found 343.1564。
Example 82
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -13, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -48; the reaction time was 20h, and the desired product was obtained as (VIII) -48 in 49% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 8.06-7.87 (m, 2H), 7.50-7.43 (m, 1H), 7.41-7.26 (m, 8H), 7.21 (dq, j=7.8, 2.7hz, 1H), 7.10 (d, j=7.9 hz, 3H), 4.77 (t, j=7.0 hz, 1H), 2.54 (d, j=7.2 hz, 1H), 2.44-2.15 (m, 6H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.74,170.52,138.93,136.61,135.24,133.93,133.00,129.48,129.07,128.80,128.55,128.39,127.30,120.00,52.39,34.90,29.40,20.84.
Infrared spectrum (thin film, cm) -1 )3305,3124,3060,2923,2854,2361,2341,1678,1659,1598,1531,1448,1405,1311,1260,1178,968,817,750,698,573,507。
High resolution mass spectrometry (APCI Source) calcd for C 24 H 23 NO 2 :357.1729,found 357.1722。
Example 83
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -14, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -49; the reaction time was 20h, and the desired product was obtained as (VIII) -49 in 60% yield.
Hydrogen nuclear magnetic resonance spectrum (400 mhz, deuterated chloroform) delta 8.01-7.94 (m, 2H), 7.69-7.56 (m, 4H), 7.55-7.46 (m, 2H), 7.40 (dd, j=8.4, 7.1hz, 2H), 7.32 (d, j=4.4 hz, 4H), 7.25 (q, j=4.5 hz, 1H), 4.78 (t, j=7.1 hz, 1H), 2.60-2.50 (m, 1H), 2.41 (dt, j=10.4, 6.8hz, 2H), 2.34-2.25 (m, 1H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.71,170.99,140.90,138.80,136.47,133.15,129.16,128.80,128.60,128.28,127.43,126.28,126.24,119.31,52.50,35.13,29.70,29.26.
Infrared spectrum (thin film, cm) -1 )3307,3063,2924,2854,1359,2341,1667,1604,1533,1448,1408,1320,1259,1162,1112,1066,1016,841,750,697,594,509,414。
High resolution mass spectrometry (APCI Source) calcd for C 24 H 20 F 3 NO 2 :411.1446,found 411.1438。
Example 84
This embodiment is substantially the same as embodiment 34 except that:
the 1, 3-dicarbonyl compound is shown as a formula (VI) -15, the olefin compound is shown as a formula (VII) -37,1,5-dicarbonyl compound is shown as a formula (VIII) -50; the reaction time was 20h, and the desired product was obtained in the form of (VIII) -50 in 85% yield.
Nuclear magnetic resonance hydrogen spectrum (400 mhz, deuterated chloroform) delta 7.96 (d, j=7.5 hz, 2H), 7.49 (d, j=7.6 hz, 1H), 7.40 (t, j=7.7 hz, 2H), 7.35-7.27 (m, 9H), 7.25-7.20 (m, 1H), 5.71 (d, j=6.3 hz, 1H), 4.75 (t, j=6.7 hz, 1H), 4.44 (dd, j=8.9, 5.7hz, 2H), 2.50 (dd, j=9.1, 4.9hz, 1H), 2.35-2.09 (m, 3H); nuclear magnetic resonance carbon spectrum (101 mhz, deuterated chloroform) δ 199.76,172.27,139.07,138.44,136.78,133.09,129.15,128.90,128.87,128.67,128.50,128.00,127.69,127.37,52.49,43.77,34.10,29.68.
Infrared spectrum (thin film, cm) -1 )3292,3062,3005,2922,2853,2361,2340,1676,1644,1597,1579,1539,1493,1448,1356,1301,1275,1260,1228,1158,1077,1029,750,695,573,504。
High resolution mass spectrometry (APCI Source) calcd for C 24 H 23 NO 2 :357.1729,found 357.1720。
The terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., in this application, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Although embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives, and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.

Claims (13)

1. A method for synthesizing a 1, 5-dicarbonyl compound, comprising:
under the protection of inert gas, mixing the 1, 3-dicarbonyl compound and the olefin compound in an organic solvent, and reacting under the conditions of stirring and light source irradiation under the action of a zirconium-containing catalyst to generate the 1, 5-dicarbonyl compound.
2. The method of synthesis according to claim 1, wherein the zirconium-containing catalyst comprises a first catalyst and a second catalyst, the first catalyst being ZrCl 4 、Zr(OTf 3 ) 4 、ZrBr 4 、Zr(O n Pr) 4 、ZrF 4 、ZrOCl 2 、Zr(OH) 4 、Zr(OAc) 4 、Zr[(PhO) 2 POO] 4 、Zr[( p OMePhO) 2 POO] 4 、Zr[( p ClPhO) 2 POO] 4 、Zr[( p BrPhO) 2 POO] 4 One or more of the following; the second catalyst is chiral phosphoric acid.
3. The synthetic method of claim 2 wherein the chiral phosphoric acid has the structure of formula (i):
wherein R is 1 、R 2 Each independently selected from phenyl,One of them.
4. The synthesis method according to claim 2, wherein the synthesis method of the 1, 5-dicarbonyl compound further comprises:
A step of reacting a 1, 3-dicarbonyl compound with the first catalyst and the second catalyst to generate an intermediate shown in a formula (II) before reacting the 1, 3-dicarbonyl compound with an olefin compound, and then mixing the intermediate shown in the formula (II) with the olefin compound in an inert atmosphere in the organic solvent and reacting under stirring and light source irradiation conditions to generate the 1, 5-dicarbonyl compound;
or, before the reaction of the 1, 3-dicarbonyl compound and the olefin compound, firstly reacting part of the 1, 3-dicarbonyl compound with the first catalyst and the second catalyst to generate an intermediate shown in a formula (II), and then mixing the intermediate shown in the formula (II), the other part of the 1, 3-dicarbonyl compound and the olefin compound in an inert atmosphere in the organic solvent, and reacting under stirring and light source irradiation conditions to generate the 1, 5-dicarbonyl compound;
in the formula (II), R 3 Is phenyl or phenyl containing substituent, R 4 Is phenyl or one of phenyl and C1-4 alkyl containing substituent.
5. The synthetic method according to claim 2, wherein the 1, 3-dicarbonyl compound has a structure of formula (III),
in the formula (III), R 5 Is phenyl or phenyl containing substituent, R 6 Is one of phenyl, phenyl containing substituent and C1-4 alkyl;
and/or, the olefin compound has a structure of formula (IV),
in the formula (IV), R 7 Phenyl or phenyl containing substituent;
and/or the 1, 5-dicarbonyl compound is a chiral 1, 5-dicarbonyl compound having a structure of formula (V),
in the formula (V), R 8 Is phenyl or phenyl containing substituent, R 9 Is one of phenyl, phenyl containing substituent and C1-4 alkyl, R 10 Is phenyl or phenyl containing substituent.
6. The synthetic method according to any one of claims 2 to 5, wherein the organic solvent is one or more of chloroform, dichloromethane, 1, 2-dichloroethane;
and/or, the light source is visible light;
and/or the addition amount of the first catalyst is 2.5-7.5mol%;
and/or the addition amount of the second catalyst is 10-20mol%.
7. The method of synthesis according to claim 6, wherein the organic solvent is chloroform;
and/or, the light source is a 10w 400nm LED;
and/or the first catalyst is ZrCl 4 The second catalyst is
8. The method of synthesis according to claim 1, wherein the zirconium-containing catalyst is ZrCl 4 、Zr[(PhO) 2 POO] 4 、Zr[( p OMePhO) 2 POO] 4 、Zr[( p ClPhO) 2 POO] 4 、Zr[( p BrPhO) 2 POO] 4 、Zr(O n Pr) 4 、Zr(HPO 4 ) 2 、ZrOCl 2 、Zr(OH) 4 、Zr(OAc) 4 、ZrH 2 、Cp 2 ZrCl 2 、CpZrCl 3 、( n Bu)Cp 2 CrCl 2 Indene ZrCl 2 Indene ZrCl 3 Indene 2 ZrCl 2 One or more of the following;
alternatively, the zirconium-containing catalyst comprises a first catalyst and a second catalyst, the first catalyst is ZrCl 4 The method comprises the steps of carrying out a first treatment on the surface of the The second catalyst is achiral phosphoric acid.
9. The method of claim 8, wherein the second catalyst is (Pho) 2 POOH、( p OMePhO) 2 POOH、( p ClPhO) 2 POOH、( p BrPhO) 2 One or more of POOH;
and/or, the 1, 3-dicarbonyl compound has a structure of formula (VI),
in the formula (VI), R is 11 Is phenyl or phenyl containing substituent, R 12 Is one of phenyl, phenyl containing substituent, C1-3 alkyl and amino with substituent;
and/or, the olefin compound has the structure of formula (VII),
in the formula (VII), R 13 Is one of hydrogen, phenyl, C1-8 aryl containing substituent, C1-18 alkyl and acetoxy, R 14 And R is 15 Each independently hydrogen, phenyl, C1-8 aryl containing substituents, C1-18 alkylOne of an acetoxy group;
and/or the 1, 5-dicarbonyl compound is an achiral 1, 5-dicarbonyl compound with a structure of a formula (VIII),
in the formula (VIII), R 16 Is phenyl or phenyl containing substituent, R 17 Is one of phenyl, phenyl containing substituent, C1-3 alkyl and amino with substituent, R 18 Is one of phenyl, C1-8 aryl containing substituent, C1-18 alkyl and acetoxy, R 19 And R is 20 Each independently represents one of phenyl, C1-8 aryl containing substituent, C1-18 alkyl and acetoxy.
10. The synthetic method according to claim 8, wherein the organic solvent is one or more of dichloromethane, chloroform, ethyl acetate, ethanol, acetonitrile, isopropanol, 1, 2-dichloroethane;
and/or the light source is 10W 400-440nm visible light;
and/or the adding amount of the zirconium-containing catalyst is 2-10mol%.
11. The method of synthesis according to claim 1, wherein the molar amount of the 1, 3-dicarbonyl compound is a mol, the molar amount of the olefin compound is bmol, and the a and b satisfy the following relationship: a-1/b-1=1/2, and a and b are both greater than 0.
12. A 1, 5-dicarbonyl compound represented by the general formula (V):
in the formula (V), R 8 Is phenyl or phenyl containing substituent，R 9 Is one of phenyl, phenyl containing substituent and C1-4 alkyl, R 10 Is phenyl or phenyl containing substituent.
13. Use of a 1, 5-dicarbonyl compound according to claim 12 or a pharmaceutically acceptable salt thereof, or a 1, 5-dicarbonyl compound synthesized by a synthesis method according to any one of claims 1 to 11 in the field of biological medicine or in the field of heterocyclic compound synthesis.
CN202310372682.8A 2023-04-10 2023-04-10 1, 5-dicarbonyl compound and synthesis method and application thereof Pending CN116444357A (en)

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