CN108623467A - A kind of C (sp3)-H function dough cyclization methods under photoredox catalyst system and catalyzing - Google Patents

A kind of C (sp3)-H function dough cyclization methods under photoredox catalyst system and catalyzing Download PDF

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CN108623467A
CN108623467A CN201810577319.9A CN201810577319A CN108623467A CN 108623467 A CN108623467 A CN 108623467A CN 201810577319 A CN201810577319 A CN 201810577319A CN 108623467 A CN108623467 A CN 108623467A
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alkyl
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aryl
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黄胜
徐晓莉
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Anhui Gull Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

This application discloses a kind of C (sp3) H function dough cyclization methods under photoredox catalyst system and catalyzing.Under photoredox catalyst system and catalyzing, using aryl sulfonyl chloride shown in formula III as free radical donor, recycle recovery is quenched through peroxidating with 2 alkyl shown in Formula II, 2 propargyl malonic acid ester type compound, has synthesized five-membered cyclic compound shown in a series of Formulas I.

Description

A kind of C (sp3)-H function dough cyclization methods under photoredox catalyst system and catalyzing
Technical field
The application belongs to organic synthesis field, and in particular to C (sp3)-H functional groups under a kind of photoredox catalyst system and catalyzing Change cyclization method.
Background technology
Organic photochemistry refers to the organic reaction under ultraviolet light or visible light conditions, and organic photochemistry synthesis is closed with conventional Compared at method, have the characteristics that it is environmental-friendly, sustainable, therefore have vast development prospect.Current scientific development is most Foreground, most challenging project is how more effectively to utilize solar energy.People are it is known that ultraviolet wavelength It is short, energy is high.Most of organic molecule can absorb ultraviolet light, but can apply to the purple of organic photochemistry in sunray Outer light is seldom, and ultraviolet reactor needs high investment more to limit its application in industrial production and experiment, in addition The shortcomings of organic side reaction is more under the ultraviolet light irradiation of high-energy, so organic photochemistry is towards the premise shone in visible light Lower development.
Since early stage in 20th century, the reaction of photoinduction has attract the attention of chemists.After the seventies, at this In a little photochemical reactions, with [Ru (bpy)3]2+Complex, Ir (ppy)3Complex be representative catalyst photooxidation also Original reaction is considered as one of the important tool of organic chemistry research.However, until 2008, with MacMillan, Yoon, Stephensen be representative chemist obtain breakthrough progress, using photocatalysis build new chemical bond method just by Gradually become one of the hot spot of organic synthesis, and is increasingly becoming an important branch of organic chemistry development.
The photoredox reaction of visible light-inducing has many advantages, such as that environmental-friendly, reaction condition is mild and wide due to it It is applied in organic synthesis generally.It has been reported that these reactions in, it is seen that light promote photocatalysis C (sp3)-H functional groups Change the interest that cyclization especially attracts synthetic organic chemists.However, in the photocatalysis C (sp of these reports3)-H officials In energy dough reaction, most of C (sp3)-H function dough reaction be all the position that process is quenched by reduction, and reacts generation C (the sp of nitrogen-atoms or oxygen atom must be equipped in adjacent bit by setting3) on.
Inventor proposes one kind under photoredox catalyst system and catalyzing, with virtue in the present invention by experiment of concentrating on studies Cycle is quenched through peroxidating as free radical donor, with 2- alkyl -2- propargyl malonic acid ester type compounds in base sulfonic acid chloride, synthesis A series of five-membered cyclic compound.
Invention content
It is an object of the invention to overcome the deficiencies in the prior art, a kind of mild condition, green high-efficient, simple for process is proposed Photoredox catalyst system and catalyzing under C (sp3)-H function dough cyclization methods.This method is in photoredox catalyst system and catalyzing Under, using aryl sulfonyl chloride shown in formula III as free radical donor, with 2- alkyl -2- propargyl malonates shown in Formula II Recycle recovery is quenched through peroxidating in class compound, synthesizes five-membered cyclic compound shown in a series of Formulas I.
According to the method for formula (one), prepared through the following steps：
By aryl sulfonyl chloride, light shown in 2- alkyl -2- propargyl malonic acid ester type compound, formula III shown in Formula II Catalyst, alkali and organic solvent are added in reactor, anti-under room temperature and 36W energy-saving lamp irradiation conditions with inert atmosphere protection It answers, monitoring reaction through TLC plates carries out completely.It is post-treated after the completion of reaction to obtain target product shown in Formulas I.
According to method shown in formula (one), in Formula II and/or Formulas I, two R1 groups are each independently selected from C1-10Alkyl；Preferably, two R1Group is each independently selected from C1-6Alkyl；Most preferably, two R1Group is each independently Selected from methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl.
According to method shown in formula (one), in Formula II and/or Formulas I, R2、R3It is each independently selected from hydrogen, C1-10Alkane Base, C6-20Aryl-C1-6Alkyl, C6-20Aryl.Preferably, R2、R3It is each independently selected from methyl, ethyl, propyl, benzyl, benzene Base.
According to method shown in formula (one), in Formula II and/or Formulas I, R4Indicate hydrogen, C1-10Alkyl, substitution do not take The C in generation6-20Aryl.Wherein the substituent group is halogen, C1-6Alkyl, C1-6Alkoxy, nitro, cyano, C1-6Acyl group.It is excellent Selection of land, R4Indicate hydrogen, C1-6Alkyl, substituted or unsubstituted phenyl, wherein substituent group are halogen, C1-6Alkyl, C1-6Alcoxyl Base, nitro, cyano, C1-6Acyl group.
According to method shown in formula (one), in formula III and/or Formulas I, Ar indicates substituted or unsubstituted C6-20Virtue Base, wherein the substituent group is halogen, C1-6Alkyl, C1-6Alkoxy, nitro, cyano, C1-6Acyl group.Preferably, Ar is indicated Phenyl, naphthalene, substituted or unsubstituted phenyl, wherein substituent group are halogen, C1-6Alkyl, C1-6Alkoxy, nitro, cyano, C1-6Acyl group.
In the preparation method stated before this invention, the photochemical catalyst is Ir (ppy)3Complex, catalyst feed intake Amount is the 1mol%-5mol%, preferably 3mol% of Formula II compound inventory.
In the preparation method stated before this invention, the alkali can be selected from sodium carbonate, potassium carbonate, sodium bicarbonate, three second Any one in amine, pyridine, 2,6- lutidines.Preferably, the alkali is sodium carbonate.
In the preparation method stated before this invention, the one kind of the organic solvent in acetonitrile, dichloromethane.It is preferred that Ground, the organic solvent are acetonitrile.The usage amount of solvent does not limit particularly, reaction raw materials can be made fully dispersed i.e. It can.
In the preparation method stated before this invention, the inert atmosphere refers to argon atmospher atmosphere or nitrogen atmosphere, from economy Angle consideration, preferably nitrogen atmosphere.
In the preparation method stated before this invention, 2- alkyl -2- propargyls malonic acid esters chemical combination shown in the Formula II The molar ratio of aryl sulfonyl chloride, alkali shown in object, formula III is 1:1-5:1-3.Preferably, 2- alkyl -2- shown in Formula II The molar ratio of aryl sulfonyl chloride, alkali shown in propargyl malonic acid ester type compound, formula III is 1:3:2-3.
In the preparation method stated before this invention, the reaction time can be determined by TLC or GC monitorings.Inventor By test of many times, determine that best reaction time range is 6-48 hours, most preferably 12-24 hours.
In the preparation method stated before this invention, the post-processing operation is as follows：After the completion of reaction, filtered with filter paper, Recycle the catalyst Ir (ppy) on filter paper3.Mother liquor Rotary Evaporators distilling off solvent, with normal hexane/acetic acid of proper proportion Ethyl ester is mobile phase, and target product is obtained through column chromatography purification ＆ isolation.
Beneficial effects of the present invention are as follows：
1. the present invention report for the first time under photoredox catalyst system and catalyzing, using aryl sulfonyl chloride shown in formula III as Free radical donor is quenched recycle recovery through peroxidating with 2- alkyl -2- propargyl malonic acid ester type compounds shown in Formula II, obtains To the synthesis strategy of five-membered cyclic compound shown in a series of Formulas I, this method is not seen in prior art report.
2. the method for the present invention has, reaction condition is mild, can carry out at room temperature, easy to operate, at low cost, catalysis The advantages of agent can recycle and reuse, environmental-friendly, high income.
Specific implementation mode
Below in conjunction with specific embodiment, further detailed description is carried out to the present invention.
In the present invention, unless otherwise instructed, reagent used can be obtained by commercially available form.Wherein, described 2- alkyl -2- propargyl malonic acid esters raw materials of compound can be by method disclosed in the prior art for example shown in Formula II Tetrahedron Letters 57 (2016) 5065-5069 are prepared.
Embodiment 1-10 reaction condition optimizations are tested
With shown in 2- alkyl -2- propargyl malonic acid ester type compounds shown in Formula II -1 and formula III -1 to nitre benzene sulphur Acyl chlorides is reaction raw materials, has inquired into influence of the differential responses condition for optimization of synthesis result, and selecting wherein has generation The embodiment 1-10 of table.As a result as shown in Table 1.
The operation of wherein embodiment 1 is as follows：
By 2- alkyl -2- propargyl malonic acid ester type compound 1 (63.2mg, 0.2mmol) shown in II-1, -1 institute of Formula II The 4-Nitrobenzenesulfonyl chloride (132mg, 0.6mmol) shown, Ir (ppy)3(4mg, 3mol%), Na2CO3(53mg, 0.5mmol), nothing Water-acetonitrile (1mL) is added in reactor, makees protective gas with argon gas, and under room temperature, 36W energy-saving lamp irradiation conditions, reaction 36 is small When, reaction is monitored by TLC plates and is carried out completely.It is filtered with filter paper after reaction fully, collects the catalyst Ir (ppy) on filter paper3。 Mother liquor Rotary Evaporators distilling off solvent is mobile phase with normal hexane/ethyl acetate of proper proportion, through column chromatography purification point From i.e. obtain the target compound I-1 of faint yellow oily, yield 89%.LRMS (70 ev of EI) m/z (%):437(M+,16), 363 (100), 290 (64).
Table one：
Embodiment Reaction condition (variable) Detach yield [%]
1 ---- 89
2 Eosin Y replace Ir (ppy)3 0
3 Ru(bpy)3Cl2·6H2O replaces Ir (ppy)3 12
4 It is added without Na2CO3 73
5 DMSO replaces acetonitrile Trace
6 Toluene replaces acetonitrile Trace
7 Temperature is 45 DEG C 91
8 It is placed in dark surrounds 0
9 Ir(ppy)31st recycling 82
10 Ir(ppy)32nd recycling 78
Wherein, the concrete operations of embodiment 2-10 are in addition to variable and the embodiment 1 listed by above-mentioned table one differ, remaining Operation is same as Example 1.
As can be seen from the above-described embodiment, other two kinds of common photochemical catalyst Eosin Y and Ru (bpy)3Cl2· 6H2O cannot be such that reaction is smoothed out, and even cannot get target product (embodiment 2-3), thus it is speculated that it may be due to excitation Two kinds of lower reasons of photochemical catalyst potential of state.Reaction can also carry out (embodiment 4) without using alkali, solvent Influence highly significant of the type for reaction, other solvents such as DMSO, toluene substitute anhydrous acetonitrile and are only capable of detecting life by GC At the product (embodiment 5-6) of trace.Raising reaction temperature appropriate may advantageously facilitate reaction and carry out, it is contemplated that energy saving to subtract Row, still selects room temperature as optimal reaction temperature (embodiment 7).Illumination condition is necessary, is reacted in dark conditions It cannot carry out (embodiment 8).After catalyst recycling twice, remain able to obtain higher target product yield (embodiment 9-10)。
As can be seen from the above-described embodiment, best reaction condition is the reaction condition of embodiment 1, i.e. photochemical catalyst selects Ir(ppy)3, to select sodium bicarbonate, reaction dissolvent for anhydrous acetonitrile, reaction condition be to be carried out under room temperature and illumination condition to alkali. On the basis of obtaining optimum reaction condition, inventor further under the optimum reaction condition, selects the reaction of different substituents Raw material is to prepare five-membered cyclic compound shown in various Formulas I.
Embodiment 11
Using parachloroben-zenesulfonyl chloride as free radical donor, with embodiment 1, the yield of target product I-2 is 76% for remaining operation.
Embodiment 12
Using to cyanobenzenesulfonyl chloride, as free radical donor, with embodiment 1, the yield of target product I-3 is for remaining operation 84%.
Embodiment 13
Using benzene sulfonyl chloride as free radical donor, with embodiment 1, the yield of target product I-4 is 61% for remaining operation.
Embodiment 14
Using benzene sulfonyl chloride as free radical donor, with embodiment 1, the yield of target product I-5 is 56% for remaining operation.
Embodiment 14
Using the compound of Formula II -2 as raw material, with embodiment 1, the yield of target product I-6 is 63% for remaining operation.
Embodiment 15
Using the compound of Formula II -3 as raw material, with embodiment 1, the yield of target product I-7 is 75% for remaining operation.
Embodiment described above is merely a preferred embodiment of the present invention, and the simultaneously exhaustion of the feasible implementation of non-present invention.For It is any apparent to made by it under the premise of without departing substantially from the principle of the invention and spirit for those skilled in the art Change, should all be contemplated as falling with the present invention claims within.

Claims (8)

1. a kind of C (sp3)-H function dough cyclization methods under photoredox catalyst system and catalyzing, which is characterized in that the side Method includes the following steps：By aryl sulphur shown in 2- alkyl -2- propargyl malonic acid ester type compound, formula III shown in Formula II Acyl chlorides, photochemical catalyst, alkali and organic solvent are added in reactor, with inert atmosphere protection, in room temperature and the energy saving light irradiation items of 36W It is reacted under part, monitoring reaction through TLC plates carries out completely, post-treated after the completion of reaction to obtain target product shown in Formulas I；
In Formula II and/or Formulas I, two R1Group is each independently selected from C1-10Alkyl；
In Formula II and/or Formulas I, R2、R3It is each independently selected from hydrogen, C1-10Alkyl, C6-20Aryl-C1-6Alkyl, C6-20Aryl；
In Formula II and/or Formulas I, R4Indicate hydrogen, C1-10Alkyl, substituted or unsubstituted C6-20Aryl, wherein the substituent group is Halogen, C1-6Alkyl, C1-6Alkoxy, nitro, cyano, C1-6Acyl group；
In formula III and/or Formulas I, Ar indicates substituted or unsubstituted C6-20Aryl, wherein the substituent group is halogen, C1-6's Alkyl, C1-6Alkoxy, nitro, cyano, C1-6Acyl group；
Wherein,
The photochemical catalyst is Ir (ppy)3；
The organic solvent is anhydrous acetonitrile.
2. according to the method described in claim 1, it is characterized in that, two R1Group is each independently selected from C1-6Alkyl, preferably Ground, two R1Group is each independently selected from methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl；
R2、R3It is each independently selected from methyl, ethyl, propyl, benzyl, phenyl；
R4Indicate hydrogen, C1-6Alkyl, substituted or unsubstituted phenyl, wherein substituent group are halogen, C1-6Alkyl, C1-6Alkoxy, Nitro, cyano, C1-6Acyl group；
Ar indicates phenyl, naphthalene, substituted or unsubstituted phenyl, and wherein substituent group is halogen, C1-6Alkyl, C1-6Alkoxy, Nitro, cyano, C1-6Acyl group.
3. method according to claim 1 or 2, which is characterized in that the alkali can be selected from sodium carbonate, potassium carbonate, carbon Any one in sour hydrogen sodium, triethylamine, pyridine, 2,6- lutidines, preferably, the alkali be sodium carbonate.
4. according to the method described in claim 1-3 any one, which is characterized in that the photochemical catalyst is Ir (ppy)3Throwing Doses is the 1mol%-5mol%, preferably 3mol% of Formula II compound inventory.
5. according to the method described in claim 1-3 any one, which is characterized in that 2- alkyl -2- alkynes shown in the Formula II The molar ratio of aryl sulfonyl chloride, alkali shown in propylmalonic acid ester type compound, formula III is 1:1-5:1-3.
6. according to the method described in claim 5, it is characterized in that, 2- alkyl -2- propargyl malonic acid esters shown in Formula II The molar ratio of aryl sulfonyl chloride, alkali shown in compound, formula III is 1:3:2-3.
7. according to the method described in claim 1-3 any one, which is characterized in that the operation of the post-processing is as follows：Instead It after the completion of answering, is filtered with filter paper, recycles the catalyst Ir (ppy) on filter paper3, mother liquor Rotary Evaporators distilling off solvent obtains It is then mobile phase with normal hexane/ethyl acetate to residue, target product is obtained through column chromatography purification ＆ isolation.
8. according to the method described in claim 1-3 any one, which is characterized in that the inert atmosphere be argon gas atmosphere or Nitrogen atmosphere.
CN201810577319.9A 2018-06-06 2018-06-06 A kind of C (sp3)-H function dough cyclization methods under photoredox catalyst system and catalyzing Pending CN108623467A (en)

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Cited By (1)

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CN109956854A (en) * 2019-04-30 2019-07-02 湖南第一师范学院 A kind of preparation method of 7- methoxyl group -3- phenyl -1,2- dihydronaphthalene

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CN106831530A (en) * 2016-12-29 2017-06-13 兰州大学 A kind of method that generation based on acyl group free radical prepares disubstituted Oxoindole
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Publication number Priority date Publication date Assignee Title
CN109956854A (en) * 2019-04-30 2019-07-02 湖南第一师范学院 A kind of preparation method of 7- methoxyl group -3- phenyl -1,2- dihydronaphthalene
CN109956854B (en) * 2019-04-30 2022-01-14 湖南第一师范学院 Preparation method of 7-methoxy-3-phenyl-1, 2-dihydronaphthalene

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