CN115583864A - Preparation method of homoallylic alcohol compound - Google Patents
Preparation method of homoallylic alcohol compound Download PDFInfo
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- CN115583864A CN115583864A CN202211126927.0A CN202211126927A CN115583864A CN 115583864 A CN115583864 A CN 115583864A CN 202211126927 A CN202211126927 A CN 202211126927A CN 115583864 A CN115583864 A CN 115583864A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07B53/00—Asymmetric syntheses
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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Abstract
The invention relates to a preparation method of a homoallylic alcohol compound, wherein a reaction substrate is
The reaction formula is as follows:
in the formula: r in the reaction substrate is phenyl, 4-chlorphenyl, 3-chlorphenyl or 4-fluorophenylAny one of 4-methylphenyl and 2-methylphenyl; organic solvent: toluene; the catalyst is a self-supported chiral phosphoric acid catalyst. The method realizes a series of asymmetric allyl reactions of substituent aldehyde in an allyl boronic acid pinacol ester/toluene system by using a self-supported chiral phosphoric acid catalyst, the yield of a target product is as high as 97%, and the enantioselectivity can reach 96% ee.
Description
Technical Field
The invention relates to the field of synthesis of homoallylic alcohol compounds, and particularly relates to a preparation method of homoallylic alcohol compounds.
Background
The homoallylic alcohol compounds are an important chemical substance and are important intermediates for synthesizing certain natural products, medicaments, spices and pesticides. In recent years, the compounds have high research value and application prospect due to the structure and biological activity thereof, and the compounds attract great attention in the fields of pharmacy and organic synthetic chemistry. As shown in figure 1, the compound is four natural molecules and drugs containing homoallylic alcohol skeletons.
Among them, the asymmetric allylation reaction of aldehyde is an important method for synthesizing homoallylic alcohol compounds. In the last decades, most of the work related to asymmetric allyl reaction of aldehyde has focused on the use of stoichiometric amount of chiral reagent or medium, however, these methods have limitations, such as the use of stoichiometric amount of chiral inducer, the difficult preparation of allylation reagent sensitive to air or moisture, and the need of using metal catalyst, such as tin, which results in the formation of toxic by-products.
Therefore, it is important to find a mild and efficient method for synthesizing homoallylic alcohol compounds.
Disclosure of Invention
Aiming at the prior art, the invention develops a preparation method of a homoallylic alcohol compound, which realizes a series of asymmetric allylic reactions of substituent aldehyde in an allylboronic acid pinacol ester/toluene system by using a self-supported chiral phosphoric acid catalyst, wherein the yield of a target product is as high as 97%, and the enantioselectivity can reach 96% ee.
Based on the above, the invention provides a preparation method of a homoallylic alcohol compound,
the reaction substrate is
The general reaction formula is as follows:
in the formula:
r in the reaction substrate is any one of phenyl, 4-chlorphenyl, 3-chlorphenyl, 4-fluorophenyl, 4-methylphenyl and 2-methylphenyl;
organic solvent: toluene.
Further, the catalyst used in the reaction general formula is a self-supported chiral phosphoric acid catalyst;
the structural formula of the self-supported chiral phosphoric acid catalyst is shown as follows,
wherein n is more than or equal to 2; ar is
i-Pr is isopropyl group, and Ph is an aromatic hydrocarbon group.
Further, the invention comprises at least the following steps:
under the protection of inert gas, adding a reaction substrate, a self-supported chiral phosphoric acid catalyst, an organic solvent and allyl boronic acid pinacol ester into a reaction tube for reaction to obtain a reaction crude product;
and removing the organic solvent from the reaction crude product, and quickly purifying by a column to obtain a target product.
Further, the reaction temperature is-25 to-35 ℃; the reaction time is 12-14h.
Further, the yield of the objective product was 90-97%, and the enantioselectivity could be up to 96% ee.
Further, the mass ratio of the reaction substrate to the self-supported chiral phosphoric acid catalyst is 18-24.
Further, the mass ratio of the reaction substrate to the self-supported chiral phosphoric acid catalyst is 20.
Further, the mass ratio of the reaction substrate to the allylboronic acid pinacol ester was 1:1-1.5.
Further, the amount of the organic solvent is 1 to 2 ml per 0.1mmol of the reaction substrate.
The homoallylic alcohol compound is any one of 1-phenyl-3-buten-1-ol, 1- (4-chlorophenyl) -3-buten-1-ol, 1- (3-chlorophenyl) -3-buten-1-ol, 1- (4-fluorophenyl) -3-buten-1-ol, 1- (4-methylphenyl) -3-buten-1-ol, and 1- (2-methylphenyl) -3-buten-1-ol.
In conclusion, the invention has the following beneficial effects:
1. the invention develops a preparation method of a homoallylic alcohol compound, which realizes a series of asymmetric allylic reactions of substituent aldehyde in an allylboronic acid pinacol ester/toluene system by using a self-supported chiral phosphoric acid catalyst, wherein the yield of a target product is as high as 97%, and the enantioselectivity can reach 96% ee.
2. In the preparation method of the homoallylic alcohol compound, aldehydes with different substituents have no obvious change on the yield and the enantioselectivity of the product, and higher yield and enantioselectivity can be obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is the structural formula of four kinds of natural molecules and drugs containing homoallylic alcohol skeleton in the background art.
Fig. 2 is structural formulas of target products N1 to N6 in the first to sixth embodiments of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials and reagents used in the following examples, etc., are commercially available unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean value or the mean value ± standard deviation of the three replicates.
In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, and includes a technical scheme a, a technical scheme B, and a technical scheme that a and B meet simultaneously; in addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a preparation method of a homoallylic alcohol compound,
the reaction substrate is
The reaction formula is as follows:
in the formula:
r in the reaction substrate is any one of phenyl, 4-chlorphenyl, 3-chlorphenyl, 4-fluorophenyl, 4-methylphenyl and 2-methylphenyl;
organic solvent: toluene.
Wherein, the catalyst used in the examples of the present application is a self-supported chiral phosphoric acid catalyst;
the structural formula of the self-supported chiral phosphoric acid catalyst is shown in the specification
n is more than or equal to 2. The preparation method comprises the following steps:
s1, 1mmol of compound-1 and 10mmol of poly (4-vinylpyridine) were taken up and added to a dry Schlenk tube, followed by drying under vacuum for 1h to give a mixture. The structure of compound-1 is:
s2, under the nitrogen atmosphere, adding 5mLCH 2 Cl 2 And 3mmol of POCl 3 Adding to the mixture obtained in step S1, reacting at 30 ℃ for 40h, filtering the mixture through cotton to remove poly (4-vinylpyridine); the solvent was then evaporated to give a pale yellow intermediate; the intermediate was used as crude without further purification;
wherein the structural formula of the generated intermediate is as follows:
s3 in the nitrogenUnder the atmosphere, 160mg of AlCl is taken 3 77mg of the intermediate formed in step S2, 1mL of CHCl was added 3 In the solution, the solution is magnetically stirred for 48 hours at the temperature of 58 ℃, then is kept stand, and the crude product is taken out and precipitated.
And S4, washing the precipitate crude product obtained in the step S3 with ethanol once, washing the precipitate crude product with 6mol/L HCl solution twice and washing the precipitate crude product with ethanol three times in sequence, performing Soxhlet extraction on the precipitate crude product with ethanol for 24 hours, and drying the precipitate crude product in a vacuum oven at 75 ℃ for 24 hours to obtain a black solid which is a self-supported chiral phosphoric acid catalyst, wherein the yield of the catalyst is 99%.
Example one
In this example, the reaction substrate was benzaldehyde, and the organic solvent was toluene; the structural formula of the self-supported chiral phosphoric acid catalyst is as follows:
the specific reaction steps are as follows:
s1, adding 0.1mmol of freshly distilled benzaldehyde and 0.005mmol of self-supported chiral phosphoric acid catalyst into a dry reaction tube, and pumping and filling nitrogen for three times; under the protection of nitrogen, 1.5mL of anhydrous toluene is added; cooling the reaction system to-30 ℃, dropwise adding 0.12mmol of allyl boronic acid pinacol ester, then stirring at the temperature for 12h, and obtaining a crude reaction product after the completion of the reaction is confirmed by NMR;
and S2, removing the organic solvent in the reaction crude product, and quickly passing through a column for purification to obtain a target product. The target product produced is 1-phenyl-3-buten-1-ol, noted as N1.
Wherein, the yield is 96%, the enantioselectivity is 95% ee.
And (3) characterizing the target product N1.
Characterization data:
1 H NMR(400MHz,CDCl 3 ):δ7.43-7.32(m,4H),7.33-7.23(m,1H),5.90-5.72(m,1H),5.22-5.10(m,2H),4.74(dd,J＝5.4,7.6Hz,1H),2.61-2.41(m,2H),2.01(br s,1H)。
13 C NMR(101MHz,CDCl 3 ):δ144.0,134.6,128.6(×2),127.7,126.0(×2),118.6,73.4,44.0。
the second embodiment is different from the first embodiment in that: the reaction substrate is 4-chlorobenzaldehyde, and the generated target product is 1- (4-chlorphenyl) -3-butene-1-ol which is marked as N2. Wherein, the yield is 95%, the enantioselectivity is 94% ee.
Characterization data:
1 H NMR(400MHz,CDCl 3 ):δ7.39-7.19(m,4H),5.92-5.64(m,1H),5.2-5.08(m,2H),4.71(dd,J＝5.1,7.7Hz,1H),2.60-2.34(m,2H),2.16(br s,1H)。
13 C NMR(101MHz,CDCl 3 ):δ142.4,134.1,133.3,128.7(×2),127.3(×2),119.0,72.7,44.0。
the third embodiment is different from the first embodiment in that: the reaction substrate is 3-chlorobenzaldehyde, and the generated target product is 1- (3-chlorphenyl) -3-butene-1-ol which is marked as N3. Wherein, yield 90%, enantioselectivity 96% ee.
1 H NMR(400MHz,CDCl 3 ):δ7.35(s,1H),7.28-7.18(m,3H),5.93-5.56(m,1H),5.26-5.06(m,2H),4.68(dd,J＝5.1,7.7Hz,1H),2.57-2.38(m,2H),2.32(br s,1H)。
13 C NMR(101MHz,CDCl 3 ):δ146.0,134.4,134.0,129.8,127.7,126.1,124.1,119.0,72.7,43.9。
The fourth embodiment is different from the first embodiment in that: the reaction substrate is 4-fluorobenzaldehyde, and the generated target product is 1- (4-fluorophenyl) -3-buten-1-ol, which is marked as N4. Wherein, the yield is 97%, the enantioselectivity is 92% ee.
1 H NMR(400MHz,CDCl 3 ):δ7.39-7.27(m,2H),7.12-7.96(m,2H),5.94-5.67(m,1H),5.24-5.06(m,2H),4.72(dd,J＝5.3,7.67Hz,1H),2.65-2.35(m,2H),2.09(br s,1H)。
13 C NMR(101MHz,CDCl 3 ):δ162.2(d,J＝245.2Hz),139.7(d,J＝3.1Hz),134.3,127.6(d,J＝8.1Hz,×2),118.7,115.3(d,J＝21.4Hz,×2),72.8,44.0。
The fifth embodiment is different from the first embodiment in that: the reaction substrate is 4-methylbenzaldehyde, and the generated target product is 1- (4-methylphenyl) -3-buten-1-ol, and is marked as N5. Wherein, the yield is 97%, the enantioselectivity is 95% ee.
1 H NMR(400MHz,CDCl 3 ):δ7.28-7.13(m,4H),5.94-5.67(m,1H),5.25-5.09(m,2H),4.71(dd,J＝5.9,7.0Hz,1H),2.51(tt,J＝1.0,6.4Hz,2H),2.35(s,3H),1.97(br s,1H)。
13 C NMR(101MHz,CDCl 3 ):δ141.0,137.2,134.7,129.2(×2),125.9(×2),118.2,73.3,43.8,21.2。
The sixth embodiment is different from the first embodiment in that: the reaction substrate is 2-methyl benzaldehyde, and the generated target product is 1- (2-methylphenyl) -3-butene-1-ol which is marked as N6. Wherein, yield 95%, enantioselectivity 95% ee.
1 H NMR(400MHz,CDCl 3 ):δ7.57-7.48(m,1H),7.25(td,J＝1.7,7.4Hz,1H),7.19(td,J＝1.4,7.4Hz,1H),7.19-7.15(m,1H),5.96-5.82(m,1H),5.27-5.16(m,2H),4.97(dd,J＝4.5,8.3Hz,1H),2.59-2.43(m,2H),2.35(s,3H),2.07(br s,1H)。
13 C NMR(101MHz,CDCl 3 ):δ142.0,134.8,134.4,130.4,127.2,126.3,125.2,118.2,69.7,42.6,19.1。
The structural formulas of the target products in the first to sixth examples are shown in fig. 2.
In summary, the present invention has developed a method for preparing homoallylic alcohols by using self-supported chiral phosphoric acid catalyst to achieve asymmetric allylic reaction of a series of substituent aldehydes in allylboronic acid pinacol ester/toluene system, with yield of the target product as high as 97%, and enantioselectivity as high as 96% ee.
All possible combinations of the technical features of the above embodiments may not be described in the above embodiments for the sake of brevity, however, the combination of the technical features should be considered as the scope of the present specification unless there is any conflict between the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for preparing homoallylic alcohol compounds is characterized in that,
the reaction substrate is
The reaction formula is as follows:
in the formula:
r in the reaction substrate is any one of phenyl, 4-chlorphenyl, 3-chlorphenyl, 4-fluorophenyl, 4-methylphenyl and 2-methylphenyl;
organic solvent: toluene.
2. The method for preparing a homoallylic alcohol compound of claim 1, wherein: the catalyst used in the reaction general formula is a self-supported chiral phosphoric acid catalyst;
the structural formula of the self-supported chiral phosphoric acid catalyst is shown as follows,
wherein n is more than or equal to 2; ar is
i-Pr is isopropyl group, and Ph is an aromatic hydrocarbon group.
3. The method for preparing a homoallylic alcohol compound of claim 2, wherein: at least comprises the following steps:
under the protection of inert gas, adding a reaction substrate, a self-supported chiral phosphoric acid catalyst, an organic solvent and allyl boronic acid pinacol ester into a reaction tube for reaction to obtain a reaction crude product;
and removing the organic solvent from the reaction crude product, and quickly purifying by a column to obtain a target product.
4. The method for preparing a homoallylic alcohol compound according to claim 3, wherein: the reaction temperature is-25 to-35 ℃; the reaction time is 12-14h.
5. The method for preparing a homoallylic alcohol compound according to claim 3, wherein: the yield of the desired product is 90-97%, the enantioselectivity can be 96% ee.
6. The method for preparing a homoallylic alcohol compound according to claim 3, wherein: the mass ratio of the reaction substrate to the self-supported chiral phosphoric acid catalyst is 18-24.
7. The method for preparing a homoallylic alcohol compound according to claim 6, wherein: the mass ratio of the reaction substrate to the self-supported chiral phosphoric acid catalyst is 20.
8. The method for preparing a homoallylic alcohol compound according to claim 3, wherein: the mass ratio of the reaction substrate to the allylboronic acid pinacol ester is 1:1-1.5.
9. The method for preparing a homoallylic alcohol compound according to claim 3, wherein: the amount of the organic solvent is 1 to 2 ml per 0.1mmol of the reaction substrate.
10. The method for preparing a homoallylic alcohol compound according to claim 3, wherein: the homoallylic alcohol compound is any one of 1-phenyl-3-buten-1-ol, 1- (4-chlorphenyl) -3-buten-1-ol, 1- (3-chlorphenyl) -3-buten-1-ol, 1- (4-fluorophenyl) -3-buten-1-ol, 1- (4-methylphenyl) -3-buten-1-ol and 1- (2-methylphenyl) -3-buten-1-ol.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366105A (en) * | 2016-08-04 | 2017-02-01 | 大连理工大学 | Preparation method and application of difluoroallyl borate |
| CN108187746A (en) * | 2017-12-25 | 2018-06-22 | 苏州大学 | Three silicon amine rare earth metal complexs are in catalysis aldehyde and the application in pi-allyl acid reaction |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366105A (en) * | 2016-08-04 | 2017-02-01 | 大连理工大学 | Preparation method and application of difluoroallyl borate |
| CN108187746A (en) * | 2017-12-25 | 2018-06-22 | 苏州大学 | Three silicon amine rare earth metal complexs are in catalysis aldehyde and the application in pi-allyl acid reaction |
Non-Patent Citations (3)
| Title |
|---|
| JINPING YUAN: "Bi(cyclopentyl)diol-Derived Boronates in Highly Enantioselective Chiral Phosphoric Acid-Catalyzed Allylation, Propargylation, and Crotylation of Aldehydes", J. ORG. CHEM., pages 12988 * |
| PANKAJ JAIN等: "Chiral Brønsted Acid-Catalyzed Allylboration of Aldehydes", J. AM. CHEM. SOC., pages 11884 * |
| XINCHUN HE: "Practical Way for the Synthesis of 3, 3’-Bis-substituted Benzo[d][1, 2]oxaphosphole 2- Oxides by Phosphonylation of in situ Generated o-Quinone Methides", TETRAHEDRON LETTERS * |
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