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Chiral aldehyde catalyst and preparation method thereof, and method for catalyzing asymmetric nucleophilic addition reaction

A catalyst and chiral technology, applied in the field of amino acid compound synthesis, can solve problems such as unfavorable step economy and unfavorable atom economy.

Active Publication Date: 2019-06-21
SOUTHWEST UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] At present, the asymmetric α-functionalization reaction of amino acid esters and their analogs mainly uses aldimines or ketimines of amino acid esters as reaction substrates. This conversion requires the use of equivalent aldehydes or ketones as protective groups, which is very important for atom economy. sexually unfavorable
In addition, this also additionally increases the steps of protecting and deprotecting groups, which is also unfavorable for the step economy

Method used

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  • Chiral aldehyde catalyst and preparation method thereof, and method for catalyzing asymmetric nucleophilic addition reaction
  • Chiral aldehyde catalyst and preparation method thereof, and method for catalyzing asymmetric nucleophilic addition reaction
  • Chiral aldehyde catalyst and preparation method thereof, and method for catalyzing asymmetric nucleophilic addition reaction

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Embodiment 1

[0056] Embodiment 1, a kind of chiral aldehyde catalyst is prepared according to the following steps:

[0057] Step ①: Dissolve 20mmol (5.72g) of (S)-1,1'-binaphthol ((S)-BINOL) in 50ml of dichloromethane, add 21mmol (3.47ml) of diisopropyl ethyl Base amine (DIPEA), cooled to -78 ° C, added 21mmol (3.44ml) of trifluoromethanesulfonic anhydride (Tf 2 (0), be warmed up to room temperature after stirring for 10min, TLC monitors the reaction, after the reaction is complete, add saturated NaHCO under ice-bath 3 solution, liquid separation to obtain an aqueous phase and an organic phase, the aqueous phase was extracted with dichloromethane, the extract and the organic phase obtained by liquid separation were combined, and anhydrous Na 2 SO 4 After drying the organic phase, the ether was purified by column chromatography (petroleum:AcOEt=30:1) to obtain about 8.04 g of compound 1, with a yield of 96%;

[0058] Step ②: Under nitrogen atmosphere, add 120mmol magnesium chips (2.88g) ...

Embodiment 2

[0101] Example 2, a method for chiral aldehyde catalyzed asymmetric nucleophilic addition reaction of amino acid derivatives, carried out according to the following steps: add α, β-unsaturated carbonyl compound, amino acid ester or amino acid ester hydrochloride to the reaction flask In, any one of the chiral aldehyde catalysts prepared in Example 1, 2,6-dicarboxypyridine, 1,5,7-triazacyclo[4.4.0]dec-5-ene (TBD ), then add 0.5ml of solvent, fully magnetically stirred at 50°C, and monitored by TLC. When the α,β-unsaturated carbonyl compound completely disappears, the entire reaction system is directly spin-dried and passed through the column (the condition of the column is petroleum ether: acetic acid Ethyl ester=10:1, wherein ethyl acetate is a liquid pure substance), obtain proline derivative, in this reaction, the number of carbon atoms of R1 and R2 of α, β-unsaturated carbonyl compound is all less than or equal to 10, amino acid ester Or the number of carbon atoms of R3 and...

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Abstract

The invention discloses a chiral aldehyde catalyst and a preparation method thereof, and a method for catalyzing an asymmetric nucleophilic addition reaction, wherein an amino acid ester or an amino acid ester hydrochloride and an alpha,beta-unsaturated carbonyl compound are added into a reaction bottle, the chiral aldehyde catalyst, 2,6-dicarboxypyridine, 1,5,7-triazacyclo[4.4.0]dec-5-ene, and anorganic solvent are sequentially added, and a complete stirring reaction is performed to perform the addition reaction. According to the present invention, the catalytic system uses the chiral aldehyde as the catalyst when the asymmetric nucleophilic addition reaction is catalyzed so as to avoid the pollution of metal ions to the product; and the asymmetric nucleophilic addition reaction method is widely used, and can achieve good effects on various alpha-beta-unsaturated ketones and various glycine esters, and the diversified synthesis of the products can easily achieve the further transformation and utilization.

Description

technical field [0001] The invention relates to the technical field of synthesis of amino acid compounds, in particular to a chiral aldehyde catalyst, a preparation method and a method for catalyzing an asymmetric nucleophilic addition reaction. Background technique [0002] Amino acid derivatives are widely used in chemistry, biology and other fields. The synthesis of natural and unnatural chiral amino acid compounds has always been an important research topic in the field of asymmetric organic synthesis. Chiral aldehydes catalyze the asymmetric α-functionalization of amino acid esters and their analogs, directly using simple primary amine amino acid compounds with unprotected amino groups as reaction substrates, which reduces the time required for catalytic systems reported so far to catalyze this chemical transformation. The steps of protecting and deprotecting the amino group are required, which is more in line with the atom economy and step economy of chemical reactions...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07C47/57C07C47/575C07C45/64C07C45/63C07C45/68C07F7/08C07B53/00C07D207/22C07D405/04C07D409/04C07D401/04
Inventor 郭其祥文巍陈磊
Owner SOUTHWEST UNIVERSITY
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