CN111153798A - Chiral gamma-hydroxybutyric acid derivative and preparation method thereof - Google Patents

Chiral gamma-hydroxybutyric acid derivative and preparation method thereof Download PDF

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CN111153798A
CN111153798A CN202010026408.1A CN202010026408A CN111153798A CN 111153798 A CN111153798 A CN 111153798A CN 202010026408 A CN202010026408 A CN 202010026408A CN 111153798 A CN111153798 A CN 111153798A
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hydroxybutyric acid
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chirality
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屠美玲
杨阿三
李琰君
贾继宁
张建庭
王祁宁
许轶
蔡金法
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Zhejiang University of Technology ZJUT
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
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    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/62—Carboxylic acid esters
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract

The invention discloses a chiralityγ-hydroxybutyric acid derivatives and a process for their preparation, the process comprising: under the catalytic action of lipase, the homoallylic alcohol compound and the acetate compound are subjected to dynamic kinetic resolution reaction in a reaction solvent, then the acrylate compound and the Grubbs reagent are sequentially added into the reaction system, olefin metathesis reaction is carried out under the catalysis of the Grubbs reagent, and finally chiral shown in the formula (1) is generatedγ-a hydroxybutyric acid derivative;
Figure 100004_DEST_PATH_IMAGE002
the invention provides a brand new chiral method by combining enzymatic dynamic kinetic resolution reaction and olefin double decomposition reactionγThe one-pot synthesis route of the (E) -hydroxybutyric acid derivative has mild reaction conditions, is favorable for reducing the equipment requirement of the preparation process, and improves the synthesis safety and synthesis safetyEconomy; secondly, the method has simple reaction process, and single configuration chirality can be obtained through one-pot reactionγ-derivatives of hydroxybutyric acid, with a very high atom economy.

Description

Chiral gamma-hydroxybutyric acid derivative and preparation method thereof
Technical Field
The invention relates to a chiral gamma-hydroxybutyric acid derivative and a preparation method thereof.
Background
Chiral hydroxy acid is an important compound with biological activity and is an important basic substance in organic synthesis. The chiral hydroxy acid is mainly used in the fields of bactericides, insecticides, anti-filtration pathogens and the like, and is widely applied in the fields of foods, medicines and cosmetics. The chiral hydroxy acid can also be used as a starting material and can be used for synthesizing various important compounds such as vitamins, antibiotics, pheromones and the like. In addition, the chiral hydroxy acid has great value as a medicine and can treat various diseases. Research shows that the medicine has curative effect on treating senile dementia and Parkinson's disease; in addition, the chiral hydroxy acid is a monomer for synthesizing biodegradable plastics, and provides an important way for solving white pollution. Therefore, the synthesis of chiral hydroxy acids has been of great interest.
At present, the synthesis method of chiral hydroxy acid mainly comprises two synthesis methods of a chemical method and a biological method. The traditional chemical synthesis method has harsh reaction conditions, and often needs high pressure, expensive catalyst and complex reaction steps; the existing biosynthesis method is often challenged by single substrate structure in the field of drug synthesis.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a chiral gamma-hydroxybutyric acid derivative and a method for preparing the same.
The chiral gamma-hydroxybutyric acid derivative is characterized in that the configuration is R-configuration, and the structural formula is as follows:
Figure BDA0002362633980000021
in the formula (1), a substituent R is phenyl, halogenated phenyl or C2-C12 alkyl; substituent R1Is C1-C3 alkyl.
The chiral gamma-hydroxybutyric acid derivative is characterized in that the optical purity of the derivative is higher than 90%.
The preparation method of the chiral gamma-hydroxybutyric acid derivative is characterized in that a homoallylic alcohol compound shown in a formula (2) and an acetate compound shown in a formula (3) are subjected to dynamic kinetic resolution reaction in a reaction solvent under the catalytic action of lipase, then an acrylate compound shown in a formula (4) and a Grubbs reagent are sequentially added into a reaction system, olefin metathesis reaction is carried out under the catalysis of the Grubbs reagent, and the chiral gamma-hydroxybutyric acid derivative shown in the formula (1) is finally generated; the reaction formula is as follows:
Figure BDA0002362633980000022
in the formulas (1) and (2), the substituent R is phenyl, halogenated phenyl or C2-C12 alkyl;
in the formula (3), the substituent R2Is C1-C3 alkyl, phenyl, halophenyl, nitro-substituted phenyl, or C1-C3 haloalkyl;
in the formulae (1) and (4), the substituent R1Is C1-C3 alkyl.
The preparation method of the chiral gamma-hydroxybutyric acid derivative is characterized in that the acetate compound shown in the formula (3) is ethyl acetate, phenol acetate, p-chlorophenol acetate, p-nitrophenol acetate or trifluoromethanol acetate, and preferably ethyl acetate.
The preparation method of the chiral gamma-hydroxybutyric acid derivative is characterized in that the feeding molar ratio of the homoallylic alcohol compound shown in the formula (2) to the acetate compound shown in the formula (3) is 1:1-1:10, and preferably 1: 3.
The preparation method of the chiral gamma-hydroxybutyric acid derivative is characterized in that the lipase is candida antarctica lipase A, candida antarctica lipase B, porcine pancreatic lipase or Amano lipase PS-IM; the reaction solvent is benzene solvent, preferably toluene, ethylbenzene or benzene.
The preparation method of the chiral gamma-hydroxybutyric acid derivative is characterized in that the time for carrying out the dynamic kinetic resolution reaction is 5-72 hours, and the temperature for carrying out the dynamic kinetic resolution reaction is 40-60 ℃.
The preparation method of the chiral gamma-hydroxybutyric acid derivative is characterized in that the acrylate compound shown in the formula (4) is methyl acrylate, ethyl acrylate or propyl acrylate.
The preparation method of the chiral gamma-hydroxybutyric acid derivative is characterized in that the Grubbs reagent is a first-generation Grubbs catalyst or a second-generation Grubbs catalyst.
The preparation method of the chiral gamma-hydroxybutyric acid derivative is characterized in that the dosage of the Grubbs reagent is 5% -25% of the mass of the homoallylic alcohol compound shown in the formula (2), and the preferential dosage is 10%.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) the invention provides a brand new one-pot synthesis route of chiral gamma-hydroxybutyric acid derivatives by combining enzymatic dynamic kinetic resolution reaction and olefin double decomposition reaction. Firstly, the method adopts a biological agent enzyme catalyst, avoids using a conventional complex noble metal catalyst in the prior art, greatly reduces the preparation cost, and simultaneously avoids the pollution of the noble metal to the environment. Secondly, compared with the traditional asymmetric catalysis, the method has mild reaction conditions, which is beneficial to reducing the equipment requirement of the preparation process and improving the synthesis safety and economy; finally, the method has simple reaction process, can obtain the chiral gamma-hydroxybutyric acid derivative with single configuration through one-pot reaction, and has very high atom economy.
2) On the basis of absorbing the respective advantages of enzymatic dynamic kinetic resolution and olefin double decomposition reaction, racemic homoallylic alcohol is used as a starting material to synthesize chiral gamma-hydroxybutyric acid by a one-pot method, the enantiomeric excess values (ee values) of the gamma-hydroxybutyric acid obtained by the reaction are both over 90 percent, and the yield is over 70 percent.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
Figure BDA0002362633980000041
1) 1-phenyl-homoallylic alcohol (0.1mmol), ethyl acetate (0.5mmol) were dissolved in 1.0mL of anhydrous toluene, followed by the addition of shov's reagent (1-hydroxytetraphenyl-cyclopentadienyl (tetraphenyl-2, 4-cyclopentadien-1-one) - μ -hydrotetracarbonyldi-ruthenium (II), CAS: 104439-77-2, the addition amount is 15% of the mass of the 1-phenyl-homoallylic alcohol), and candida antarctica lipase B (the addition amount is 30% of the mass of the 1-phenyl-homoallylic alcohol). The reaction solution was reacted at 50 ℃ for 48 hours, and then methyl acrylate (1.5 times the molar amount of 1-phenyl-homoallylic alcohol) and the first-generation Grubbs catalyst (10% by mass of methyl acrylate) were sequentially added. The reaction was heated to reflux for 48 h.
2) After the reaction, the reaction solution is filtered to remove the catalyst, and then the crude product is obtained by reduced pressure distillation.
3) The crude product was purified by column chromatography eluting with petroleum ether: ethyl acetate 5:1(v/v), 75% yield of the final product (based on 1-phenyl-homoallyl alcohol) and 92% ee of the product.
Nuclear magnetic data of the product:1H-NMR(400MHz,CDCl3,ppm)δ:7.42–7.27(m,5H),6.96(dt,J＝15.6,7.3Hz,1H),5.90(dt,J＝15.7,1.4Hz,1H),4.83(dd,J＝7.7,5.2Hz,1H),4.17(q,J＝7.1Hz,2H),2.74–2.54(m,2H),1.27(t,J＝7.1Hz,3H).
ee value detection conditions of the product: the chiral chromatographic column is xylonite AD-H, the detection wavelength is 254nm, the mobile phase is n-hexane/isopropanol 90:10(v/v), and the flow rate is 0.2 mL/min.
Example 2
Figure BDA0002362633980000051
1) 1- (4-bromo-phenyl) -homoallylic alcohol (0.1mmol), p-chlorophenol acetate (0.1mmol) were dissolved in 2.0mL of anhydrous benzene, followed by addition of shov's reagent (5% of 1- (4-bromo-phenyl) -homoallylic alcohol), Candida antarctica lipase B (30% of 1- (4-bromo-phenyl) -homoallylic alcohol). The reaction solution was reacted at 50 ℃ for 24 hours, and then methyl acrylate (1.2 times the molar amount of 1- (4-bromo-phenyl) -homoallylic alcohol) and a second-generation Grubbs catalyst (5% by mass of methyl acrylate) were sequentially added. The reaction was heated to reflux for 48 h.
2) After the reaction, the reaction solution is filtered to remove the catalyst, and then the crude product is obtained by reduced pressure distillation.
3) The crude product was purified by column chromatography eluting with petroleum ether: ethyl acetate 5:1(v/v), 80% yield of the final product (based on 1- (4-bromo-phenyl) -homoallylic alcohol) and 95% ee of the product.
Nuclear magnetic data of the product:1H-NMR(400MHz,CDCl3,ppm)δ:7.85-7.17(m,4H),6.96(dt,J＝15.6,7.3Hz,1H),5.90(dt,J＝15.7,1.4Hz,1H),4.83(dd,J＝7.7,5.2Hz,1H),4.17(q,J＝7.1Hz,2H),2.74-2.54(m,2H),1.27(t,J＝7.1Hz,3H)。
ee value detection conditions of the product: the chiral chromatographic column is xylonite AD-H, the detection wavelength is 254nm, the mobile phase is n-hexane/isopropanol 90:10(v/v), and the flow rate is 0.2 mL/min.
Example 3
Figure BDA0002362633980000061
1) 1-heptyl-homoallylic alcohol (0.1mmol) and p-nitrophenol acetate (1.0mmol) were dissolved in 5.0mL of anhydrous ethylbenzene, followed by addition of shov's reagent (10% of the amount of 1-heptyl-homoallylic alcohol added), Candida antarctica lipase B (30% of the amount of 1-heptyl-homoallylic alcohol added). The reaction solution was reacted at 50 ℃ for 72 hours, and then methyl acrylate (added in an amount of 2.0 times the molar amount of 1-heptyl-homoallyl alcohol) and the first-generation Grubbs catalyst (added in an amount of 15% by mass based on the mass of methyl acrylate) were sequentially added. The reaction was heated to reflux for 48 h.
2) After the reaction, the reaction solution is filtered to remove the catalyst, and then the crude product is obtained by reduced pressure distillation.
3) The crude product was purified by column chromatography eluting with petroleum ether: ethyl acetate 5:1(v/v), final product yield 70% (based on 1-heptyl-homoallyl alcohol) and ee value of 90% for the product.
Nuclear magnetic data of the product:1HNMR(400MHz,CDCl3,ppm)δ7.04-6.90(m,1H),5.91(dt,J＝15.6,1.4Hz,1H),4.19(q,J＝7.1Hz,2H),3.76(dt,J＝12.1,6.2Hz,1H),2.47-2.24(m,2H),1.52-1.43(m,3H),1.29(t,J＝7.1Hz,13H),0.88(t,J＝6.9Hz,3H)。
the statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.

Claims (10)

1. Chiralityγ-a hydroxybutyric acid derivative, characterized in that it has the configurationR-Configuration, structural formula as follows:
Figure DEST_PATH_IMAGE002
in the formula (1), a substituent R is phenyl, halogenated phenyl or C2-C12 alkyl; substituent R1Is C1-C3 alkyl.
2. A chirality as claimed in claim 1γ-a hydroxybutyric acid derivative characterized in that it has an optical purity higher than 90%.
3. A chirality as claimed in claim 1γThe preparation method of the (E) -hydroxybutyric acid derivative is characterized in that the homoallylic alcohol compound shown in the formula (2) and the acetate compound shown in the formula (3) are subjected to dynamic kinetic resolution reaction in a reaction solvent under the catalytic action of lipase, and then cis-hydroxy butyric acid derivative is subjected to cis-hydroxy butyric acid in a reaction systemAdding the acrylate compound shown in the formula (4) and the Grubbs reagent in turn, and carrying out olefin metathesis reaction under the catalysis of the Grubbs reagent to finally generate the chiral compound shown in the formula (1)γ-a hydroxybutyric acid derivative; the reaction formula is as follows:
Figure DEST_PATH_IMAGE004
in the formulas (1) and (2), the substituent R is phenyl, halogenated phenyl or C2-C12 alkyl;
in the formula (3), the substituent R2Is C1-C3 alkyl, phenyl, halophenyl, nitro-substituted phenyl, or C1-C3 haloalkyl;
in the formulae (1) and (4), the substituent R1Is C1-C3 alkyl.
4. A chirality as claimed in claim 3γA process for producing an (E) -hydroxybutyric acid derivative, characterized in that the acetate compound represented by formula (3) is ethyl acetate, phenol acetate, p-chlorophenol acetate, p-nitrophenol acetate, or trifluoromethanol acetate, preferably ethyl acetate.
5. A chirality as claimed in claim 3γA process for producing a hydroxybutyric acid derivative, characterized in that the molar ratio of homoallylic alcohol compound of formula (2) to acetate compound of formula (3) is 1:1 to 1:10, preferably 1: 3.
6. A chirality as claimed in claim 3γA method for producing a hydroxybutyric acid derivative, characterized in that the lipase is candida antarctica lipase a, candida antarctica lipase B, porcine pancreatic lipase or Amano lipase PS-IM; the reaction solvent is benzene solvent, preferably toluene, ethylbenzene or benzene.
7. A chirality as claimed in claim 3γProcess for the preparation of hydroxy-butanoic acid derivatives, characterized by carrying out dynamic kineticsThe time of the resolution reaction is 5-72 hours, and the temperature for carrying out the dynamic kinetic resolution reaction is 40-60 ℃.
8. A chirality as claimed in claim 3γA process for producing a hydroxybutyric acid derivative, characterized in that the acrylate compound represented by formula (4) is methyl acrylate, ethyl acrylate or propyl acrylate.
9. A chirality as claimed in claim 3γ-a process for the preparation of hydroxybutyric acid derivatives, characterized in that said Grubbs reagent is a first generation Grubbs catalyst or a second generation Grubbs catalyst.
10. A chirality as claimed in claim 3γProcess for the preparation of (E) -hydroxybutyric acid derivatives, characterized in that the Grubbs' reagent is used in an amount of 5% to 25%, preferably 10%, of the amount of homoallylic alcohol compound of formula (2).
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56161347A (en) * 1980-05-19 1981-12-11 Agency Of Ind Science & Technol Polyprenylcarboxylic acid derivative and its preparation
CN1484631A (en) * 2000-11-14 2004-03-24 西巴特殊化学品控股有限公司 Preparation of enantiomerically pure hydroxy esters and acids
CN1918108A (en) * 2004-02-12 2007-02-21 吉万奥丹股份有限公司 3-(2-alkoxycarbonyloxy-phenyl) acrylic acid esters and their use as precursors for the delivery of olfactory compounds
CN104402718A (en) * 2014-11-07 2015-03-11 同济大学 Chiral allyl ester compound and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56161347A (en) * 1980-05-19 1981-12-11 Agency Of Ind Science & Technol Polyprenylcarboxylic acid derivative and its preparation
CN1484631A (en) * 2000-11-14 2004-03-24 西巴特殊化学品控股有限公司 Preparation of enantiomerically pure hydroxy esters and acids
CN1918108A (en) * 2004-02-12 2007-02-21 吉万奥丹股份有限公司 3-(2-alkoxycarbonyloxy-phenyl) acrylic acid esters and their use as precursors for the delivery of olfactory compounds
CN104402718A (en) * 2014-11-07 2015-03-11 同济大学 Chiral allyl ester compound and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
AMY A. OTT ET AL.: "Evidence for a Sigmatropic and an Ionic Pathway in the Winstein Rearrangement", 《J. ORG. CHEM.》 *
JUN-SEOP IM ET AL.: "Reaction characteristics of the dynamic kinetic resolution of 1-phenylethanol over Ru complexes immobilized on PTA-modified γ-alumina and Novozym 435", 《CHEMICAL ENGINEERING JOURNAL》 *
L.THIJS ET AL.: "A general stereospecific synthesis of γ-hydroxy-α,β-unsaturated esters", 《TETRAHEDRON LETTERS》 *
REJI N. NAIR ET AL.: "Grubbs Cross-Metathesis Pathway for a Scalable Synthesis of γ‑Keto-α,β-unsaturated Esters", 《J. ORG. CHEM.》 *

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Application publication date: 20200515