CN110563583B - Method for asymmetrically catalyzing and synthesizing optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate - Google Patents

Method for asymmetrically catalyzing and synthesizing optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate Download PDF

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CN110563583B
CN110563583B CN201810573131.7A CN201810573131A CN110563583B CN 110563583 B CN110563583 B CN 110563583B CN 201810573131 A CN201810573131 A CN 201810573131A CN 110563583 B CN110563583 B CN 110563583B
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acid
dimethyl
hydroxy
optically active
oxobutyrate
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达朝山
杜智宏
秦文娟
李玉彦
梁向明
白彦兵
林行
张连春
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Hangzhou Xinfu Science & Technology Co ltd
Lanzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B01J31/0238—Amines with a primary amino group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0241—Imines or enamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
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    • 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
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07B2200/07—Optical isomers

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Abstract

The invention discloses a method for synthesizing optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate by catalyzing asymmetric Aldol reaction of isobutyraldehyde and glyoxylate through chiral amino amide or enantiomer thereof. The method for asymmetrically catalyzing and synthesizing the optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate is shown as the formula 1:

Description

Method for asymmetrically catalyzing and synthesizing optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate
Technical Field
The invention relates to a method for synthesizing optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate by catalyzing asymmetric Aldol reaction of isobutyraldehyde and glyoxylate through chiral amino amide or enantiomer thereof.
Background
Optically active compounds are a common phenomenon in nature and play no alternative role in the course of the life activities of cells and organisms. Many drugs are optically active compounds, and chirality is an important element of a drug. Optically active 2-hydroxy-3, 3-dimethyl-4-oxobutanoic acid ester is a precursor compound of optically active pantoic acid lactone, and can be rapidly and simply synthesized by asymmetric Aldol reaction of isobutyraldehyde and glyoxylic acid ester. Around this asymmetric Aldol reaction, there have been a series of reports.
The amino acid can be used as a chiral catalyst to catalyze the asymmetric Aldol reaction, but the defect is that the using amount of the amino acid is large, and the enantioselectivity of the reaction is not ideal. For example, some researchers have used 50 mol% of amino acid as catalyst, but the product yield and ee value are low, such as: the leucine catalyzed yield was 76% and the ee value was 64%; the catalytic yield of isoleucine was 81%, the ee value was 77%; the catalytic yield of alanine was 65% and the ee value was 60%; the catalytic yield of valine was 78%, the ee value was 74%; the catalytic yield of phenylalanine was 79%, and the ee value was 72% ((Org. Lett. 2012, 14Number 8, 2180-. Relatively more studies on histidine have shown that the reaction is catalyzed directly with histidine at a yield of 70% and an ee value of 77%, and that the yield and enantioselectivity are greatly reduced to 35% and 48% ee when a histidine derivative is used as a catalyst (see (R) (R))J. Am. Chem. Soc.2012, 134, 6286−6295; J. Org. Chem.2012, 77, 2310-2330). In-line with the aboveThen, the asymmetric Aldol reaction between isobutyraldehyde and ethyl glyoxylate catalyzed by histidine is carefully optimized, the optimal enantioselectivity result catalyzed by histidine is obtained, and the ee value is only 79 percent (the highest value isJ. Org. Chem. 2015, 80, 3387-3396). In addition, no other catalysts have been reported for this reaction. Therefore, the asymmetric catalytic efficiency of the reaction has not yet reached a satisfactory state, and many pioneering works are required to improve the asymmetric catalytic efficiency.
Disclosure of Invention
The invention provides a method for asymmetric catalytic synthesis of optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate, which can overcome the defects of the prior art.
The invention relates to a method for asymmetrically catalyzing and synthesizing optically active 2-hydroxy-3, 3-dimethyl-4-oxo-butyric ester, which has a chemical reaction formula shown in formula 1:
Figure 770184DEST_PATH_IMAGE001
the synthesis process comprises the following steps: adding isobutyraldehyde, glyoxylate, a chiral catalyst Cat and an additive into a reaction vessel containing a solvent, and stirring to obtain a product, namely the optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate 1, wherein:
R1is C1 ~ C4Linear or branched alkyl, benzyl;
the chiral catalyst Cat is chiral amino amide shown as a formula 2 or an enantiomer thereof,
Figure 421745DEST_PATH_IMAGE002
wherein R is2Is C1 ~ C6Alkyl or substituted alkyl or aryl or arylmethyl of R3Is C1 ~ C4Straight or branched alkyl or phenyl of (a);
the additive is any one of acetic acid, benzoic acid, 2, 4-dinitrophenol, trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid, propionic acid, isobutyric acid, chloroacetic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and methanesulfonic acid;
the solvent is any one of n-hexane, cyclohexane, dichloromethane, chloroform, dichloroethane, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dibutyl ether, dioxane, ethyl acetate, methyl acetate, isopropyl acetate, isoamyl acetate, ethyl formate, methyl tert-butyl ether, acetonitrile, toluene, xylene, methanol, ethanol, isopropanol, and n-butanol.
Preferably, in a method for the asymmetric catalytic synthesis of an optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate according to the present invention:
R1is C1 ~ C4The linear alkyl group of (1);
the chiral catalyst Cat is chiral amino amide shown as a formula 2 or enantiomer thereof, wherein R2Is C1 ~ C4Alkyl or benzyl of R3Is C1 ~ C4The linear alkyl group of (1);
the additive is any one of acetic acid, benzoic acid, 2, 4-dinitrophenol, trifluoroacetic acid, propionic acid, isobutyric acid and chloroacetic acid;
the solvent is any one of n-hexane, dichloromethane, dichloroethane, diethyl ether, tetrahydrofuran, ethyl acetate, methyl acetate, acetonitrile, xylene, and methanol.
More preferably, in a method for the asymmetric catalytic synthesis of an optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate according to the present invention:
R1is methyl or ethyl;
the chiral catalyst Cat is any one of the chiral aminoamide shown in formula 3 or an enantiomer thereof,
Figure 873586DEST_PATH_IMAGE003
。
more preferably, in a method for the asymmetric catalytic synthesis of an optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate according to the present invention:
the chiral catalyst Cat used is (in the formula 3R）-Cat-1；
The additive is acetic acid or EtCOOH ori-any one of PrCOOH; the solvent is any one of dichloromethane or ethyl acetate or methyl acetate.
The chiral amino amide or enantiomer thereof is used as an organic micromolecular catalyst, so that the asymmetric Aldol reaction of isobutyraldehyde and glyoxylate can be catalyzed in a green and high-efficiency manner, and the 2-hydroxy-3, 3-dimethyl-4-oxobutyrate with high optical activity is synthesized, and a feasible and high-efficiency scheme is provided for solving the problem.
Detailed Description
The following examples further describe the invention in detail. However, the following examples are only for illustrating the present invention, and the details of the present invention are not limited to the following examples.
Example 1
Effect of solvent
To a 5 mL clean round-bottom flask equipped with a stirring magneton, isobutyraldehyde (5 mmol, 0.46 mL), 0.25 mL of a solvent, and a catalyst (A)R) -Cat-1 (0.025 mmol, 5.6 mg) and acetic acid (0.025 mmol, 14.3 μ L), stirring at room temperature for 10.0 min, adding ethyl glyoxylate (50% toluene solution, 0.5 mmol, 1.0 mL), stirring at room temperature for reaction, adding ethyl acetate 20 mL after TLC detection till the reaction is completed, washing with a small amount of saturated saline solution, drying over anhydrous sodium sulfate, concentrating under reduced pressure, and performing flash silica gel column chromatography with petroleum ether and ethyl acetate to obtain a reaction product (the reaction product is prepared by (the step of) (1R)-1a。
The solvent has a significant effect on the ee value of the asymmetric catalytic reaction, and the results are shown in table 1 below.
Figure 737637DEST_PATH_IMAGE004
Example 2
Effect of additives on enantioselectivity of reactions
In a 5 mL clean round bottom equipped with a stirring magnetonIn a flask, isobutyraldehyde (5 mmol, 0.46 mL) and CH were added in this order2Cl2 (0.25 mL), catalyst: (R) -Cat-1 (0.025 mmol, 5.6 mg) and additive (0.025 mmol), stirring at rt for 10.0 min, adding ethyl glyoxylate (50% toluene solution, 0.5 mmol, 1.0 mL), stirring at room temperature for reaction, detecting by TLC until the reaction is complete, adding ethyl acetate 20 mL, washing with a small amount of saturated saline solution, drying over anhydrous sodium sulfate, concentrating under reduced pressure, and purifying by silica gel flash column chromatography with petroleum ether and ethyl acetate to obtain a reaction product (A)R)-1a。
The effect of various additives on the ee value of the asymmetrically catalyzed Aldol reaction is shown in table 2 below.
Figure 20851DEST_PATH_IMAGE005
Example 3
Comparison of enantioselectivities for different catalysts.
To a 5 mL clean round-bottom flask equipped with a stirring magneton, isobutyraldehyde (5 mmol, 0.46 mL), CH were added in this order2Cl2(0.25 mL), catalyst: (R) -Cat (0.025 mmol) and acetic acid (0.025 mmol, 14.3 μ L), stirring at room temperature for 10.0 min, adding ethyl glyoxylate (50% toluene solution, 0.5 mmol, 1.0 mL), stirring at room temperature for reaction, adding ethyl acetate 20 mL after TLC detection till the reaction is completed, washing with a small amount of saturated saline solution, drying over anhydrous sodium sulfate, concentrating under reduced pressure, preparing and purifying by using petroleum ether and ethyl acetate fast silica gel column chromatography to obtain a reaction product (I: (R) (R))R)-1a。
The enantioselective catalytic effect of the three catalysts is shown in Table 3 below, the results showing that catalyst: (R) The enantioselectivity of-Cat-1 is highest.
Figure 312155DEST_PATH_IMAGE006
Example 4
In a 5 mL clean round-bottom flask equipped with a stirring magneton, isobutyraldehyde (b), (c) was added in sequence1 mmol, 92 μ L), ethyl acetate (1.0 mL), catalyst: (R) -Cat-1 (0.05 mmol, 11 mg), stirring at room temperature for 10.0 min, adding ethyl glyoxylate (50% toluene solution, 0.5 mmol, 1.0 mL), stirring at room temperature for reaction, detecting by TLC (thin layer chromatography) until the reaction is finished, adding ethyl acetate 20 mL, washing with a small amount of saturated saline solution, drying over anhydrous sodium sulfate, concentrating under reduced pressure, and performing flash silica gel column chromatography with petroleum ether and ethyl acetate to obtain a reaction product (the reaction product is prepared and purified by (1) (0.05 mmol, 11 mg))R) -1a, yield = 93%,
Figure DEST_PATH_IMAGE007
ee = 93%。1H NMR (400 MHz, ) δ 9.59 (s, 1H), 4.35 (s, 1H), 4.27 (m, 2H), 3.13 (s, 1H), 1.29 (t, J = 7.1 Hz, 3H), 1.16 (s, 3H), 1.08 (s, 3H). 13C NMR (100 MHz, ) δ 202.7, 73.6, 62.4, 50.5, 18.3, 16.9, 14.2.。
example 5
In a 5 mL clean round bottom flask equipped with a stirring magneton, isobutyraldehyde (1 mmol, 92. mu.L), ethyl acetate (1.0 mL), catalyst (C:)S) -Cat-1 (0.05 mmol, 11 mg) was stirred at room temperature for 10.0 min, ethyl glyoxylate (50% in toluene, 0.5 mmol, 1.0 mL) was added, the reaction was stirred at room temperature, after completion of the reaction by TLC, ethyl acetate (20 mL) was added, the mixture was washed with a small amount of saturated brine, and anhydrous sulfuric acid was added
Figure 270533DEST_PATH_IMAGE008
Sodium drying, vacuum concentrating, and purifying by petroleum ether and ethyl acetate rapid silica gel column chromatography to obtain reaction productS) -1a, yield = 91%, ee = 93%.1H NMR (400 MHz, ) δ 9.59 (s, 1H), 4.35 (s, 1H), 4.27 (m, 2H), 3.13 (s, 1H), 1.29 (t, J = 7.1 Hz, 3H), 1.16 (s, 3H), 1.08 (s, 3H); 13C NMR (100 MHz) δ 202.7, 73.6, 62.4, 50.5, 18.3, 16.9, 14.2.。
Example 6
In a 5 mL clean round bottom flask equipped with a stirring magneton, isobutyraldehyde (1 mmol, 92. mu.L), ethyl acetate (1.0 mL), catalyst (C:)R) -Cat-1 (0.05 mmol, 11 mg), stirring at room temperature for 10.0 min, adding methyl glyoxylate (0.5 mmol, 45 mg), stirring at room temperature for reaction, detecting by TLC until the reaction is completed, adding 20 mL of ethyl acetate, washing with a small amount of saturated sodium chloride, drying over anhydrous sodium sulfate, and concentrating under reduced pressure
Figure DEST_PATH_IMAGE009
After condensation, the reaction product is prepared and purified by quick silica gel column chromatography of petroleum ether and ethyl acetate (R) -1b, yield = 87%, ee = 78%;1H NMR (400 MHz, ) δ 9.58 (s, 1H), 4.37 (d, J = 5.9 Hz, 1H), 3.81 (s, 3H), 2.96 (d, J = 5.9 Hz, 1H), 1.16 (s, 3H), 1.08 (s, 3H); 13C NMR (150 MHz, CDCl3) δ202.5,173.3, 73.8, 52.7, 50.3,18.2, 17.1.。
example 7
In a 5 mL clean round bottom flask equipped with a stirring magneton, isobutyraldehyde (1 mmol, 92. mu.L), ethyl acetate (1.0 mL), catalyst (C:)S) -Cat-1 (0.05 mmol, 11 mg), stirring at room temperature for 10.0 min, adding methyl glyoxylate (0.5 mmol, 45 mg), stirring at room temperature for reaction, detecting by TLC until the reaction is completed, adding 20 mL of ethyl acetate, washing with a small amount of saturated sodium chloride, drying over anhydrous sodium sulfate, and concentrating under reduced pressure
Figure 141537DEST_PATH_IMAGE010
Then, petroleum ether and ethyl acetate are used for rapid silica gel column chromatography to prepare and purify a reaction product (a)S) -1b, yield = 89%, ee = 78%;1H NMR (400 MHz) δ 9.58 (s, 1H), 4.37 (d, J = 5.9 Hz, 1H), 3.81 (s, 3H), 2.96 (d, J = 5.9 Hz, 1H), 1.16 (s, 3H), 1.08 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 225.8, 202.5, 73.7, 52.7, 18.2, 17.1.。

Claims (4)

1. a method for asymmetrically catalyzing and synthesizing optically active 2-hydroxy-3, 3-dimethyl-4-oxo-butyric ester has a chemical reaction formula shown in formula 1:
Figure FDA0003509187900000011
the synthesis process comprises the following steps: adding isobutyraldehyde, glyoxylate, a compound shown as a formula 2 as a chiral catalyst Cat and an additive into a reaction vessel containing a solvent, and stirring to obtain a product, namely the optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate 1, wherein:
R1is C1～C4Linear or branched alkyl, benzyl;
R2is C1～C6Alkyl or benzyl of (a);
R3is C1～C4Linear or branched alkyl of (a);
the additive is any one of acetic acid, benzoic acid, 2, 4-dinitrophenol, trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid, propionic acid, isobutyric acid, chloroacetic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and methanesulfonic acid;
the solvent is any one of n-hexane, cyclohexane, dichloromethane, chloroform, dichloroethane, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dibutyl ether, dioxane, ethyl acetate, methyl acetate, isopropyl acetate, isoamyl acetate, ethyl formate, methyl tert-butyl ether, acetonitrile, toluene, xylene, methanol, ethanol, isopropanol, and n-butanol.
2. The process for the asymmetric catalytic synthesis of optically active 2-hydroxy-3, 3-dimethyl-4-oxobutanoic acid ester according to claim 1, wherein:
R1is C1～C4The linear alkyl group of (1);
the chiral catalyst Cat is shown as a formula 2Chiral amino amides, wherein R2Is C1～C4Alkyl or benzyl of R3Is C1～C4The linear alkyl group of (1);
the additive is any one of acetic acid, benzoic acid, 2, 4-dinitrophenol, trifluoroacetic acid, propionic acid, isobutyric acid and chloroacetic acid;
the solvent is any one of n-hexane, dichloromethane, dichloroethane, diethyl ether, tetrahydrofuran, ethyl acetate, methyl acetate, acetonitrile, xylene, and methanol.
3. The process for the asymmetric catalytic synthesis of an optically active 2-hydroxy-3, 3-dimethyl-4-oxobutanoate ester according to claim 1 or 2, wherein:
R1is methyl or ethyl;
the chiral catalyst Cat is any one of chiral amino amides shown as a formula 3
Figure FDA0003509187900000021
4. The method for the asymmetric catalytic synthesis of optically active 2-hydroxy-3, 3-dimethyl-4-oxobutyrate according to claim 3, wherein:
the chiral catalyst Cat is (R) -Cat-1 in a formula 3;
the additive is any one of acetic acid, propionic acid or isobutyric acid;
the solvent is any one of dichloromethane or ethyl acetate or methyl acetate.
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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"3-羟基-4，4- 二甲基 -1- 苯基-2- 吡咯烷酮的不对称合成";张方林等;《合成化学》;20081231;第16卷(第4期);第438-439页 *
"Electrostatic Repulsion and Hydrogen-Bonding Interactions in a Simple N-Aryl-L-valinamide Organocatalyst Control the Stereoselectivity in Asymmetric Aldol Reactions";Yuya Tanimura等;《Eur. J. Org. Chem.》;20131231;第2013卷;第6535-6539页 *
"Organocatalyzed Highly Enantioselective Aldol Reaction of Aldehydes for Synthesis of (R)-Pantolactone";Zhi-Hong Du等;《Asian J. Org. Chem》;20210331;第10卷;第1167-1172页 *

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