Single chiral center catalyst, preparation method thereof and method for catalytically synthesizing chiral alcohol compounds and chiral alpha-allyl alcohol

A chiral center and catalyst technology, which is applied in the field of catalytic synthesis of chiral alcohol compounds and chiral α-allyl alcohol, can solve the problems of large substrate scope limitation, low substrate universality, and large limitations.

Active Publication Date: 2021-04-20
SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For the chemical asymmetric catalytic synthesis, the stereoselective synthesis of aldehydes and chiral auxiliaries is usually required, which requires the participation of expensive metals and chiral auxiliaries, which has relatively large limitations and relatively high costs; and the use of enzyme catalysis for kinetic Chemical resolution of racemic allyl alcohol is a commonly used method, which utilizes the difference in the reaction rate between the reaction reagent and the alcoholic hydroxyl group to realize the kinetic resolution of racemic allyl alcohol, and the enzyme-catalyzed kinetic resolution to prepare chiral allyl Alcohols usually have high activity and strong stereospecific selectivity, but the scope of substrates is relatively limited and the universality of substrates is low

Method used

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  • Single chiral center catalyst, preparation method thereof and method for catalytically synthesizing chiral alcohol compounds and chiral alpha-allyl alcohol
  • Single chiral center catalyst, preparation method thereof and method for catalytically synthesizing chiral alcohol compounds and chiral alpha-allyl alcohol
  • Single chiral center catalyst, preparation method thereof and method for catalytically synthesizing chiral alcohol compounds and chiral alpha-allyl alcohol

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preparation example Construction

[0087] The preparation method of a class of monochiral center catalysts according to an embodiment is a preparation method of the single chiral center catalysts of the above-mentioned embodiments, comprising the following steps:

[0088] reacting the precursor with the first ligand in the first solvent to prepare the intermediate;

[0089] The catalyst is prepared by reacting the intermediate with the second ligand in a second solvent.

[0090] Wherein, the precursor is tris(triphenylphosphorus) ruthenium dichloride. Selecting the above precursors can improve the activity of the reaction.

[0091] The first ligand has the following general formula: In the formula, Z is -S-, -N=CH- or -CH=CH-. Specifically, the first ligand has the following general formula:

[0092] In the formula, R 2 One selected from a chain alkyl group and a cycloalkane group. Further, R 2 from C 1 ~C 4 The chain alkyl and C 3 ~C 6 one of the cycloalkyl groups. Preferably, R 2 from -CH 3 ,...

Embodiment 1-1

[0172] The preparation process of the monochiral center catalyst of the present embodiment is as follows:

[0173] (1) Under the protection of argon, the molar ratio of tris (triphenylphosphine) ruthenium (II) dichloride and isopropyl substituted 2-(aminomethyl) chiral pyrimidine ligand is 1:1. It was dissolved in dichloromethane, and the reaction was stirred at 25° C. for 12 h to obtain the first reaction solution. The first reaction solution is filtered to obtain a first filtrate, the first filtrate is subjected to vacuum distillation to obtain a first solid, the first solid is dissolved in dichloromethane, and n-hexane is added thereto for recrystallization to obtain an intermediate, The volume ratio of dichloromethane to n-hexane was 1:1.

[0174] (2) Combine the intermediate obtained above with 1,2-bis(diphenylphosphino)propane It was dissolved in toluene and stirred at 120° C. for 12 h to obtain a second reaction solution, wherein the molar ratio of the intermediate ...

Embodiment 1-2

[0182] The preparation process of the monochiral center catalyst of the present embodiment is as follows:

[0183] (1) Under the protection of argon, the molar ratio of tris(triphenylphosphine) ruthenium(II) dichloride and isopropyl substituted 2-(aminomethyl) chiral pyridine ligand is 1:1. Dissolved in dichloromethane, and then stirred at 25 ° C for 12 hours to obtain the first reaction solution, the first reaction solution was filtered to obtain the first filtrate, the first filtrate was distilled under reduced pressure to obtain the first solid, and the first After the solid was dissolved in dichloromethane, n-hexane was added thereto for recrystallization to obtain an intermediate, and the volume ratio of dichloromethane and n-hexane was 1:1.

[0184] (2) Combine the intermediate obtained above with (1,2-bis(3,5-di-tert-butylphenyl)-diphenylphosphino)benzene It was dissolved in toluene and stirred at 120 °C for 12 h to obtain a second reaction solution, in which the int...

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Abstract

The invention relates to a single chiral center catalyst, a preparation method thereof and a method for catalytically synthesizing chiral alcohol compounds and chiral alpha-allyl alcohol. The single chiral center catalyst has a structure as shown in the following general formula shown in the description, wherein in the formula, Z is -S-, -N = CH- or -CH = CH-. According to the catalyst, the achiral diphosphorus ligand is adopted, and chiral elements of the diamine ligand are reserved and adjusted at the same time, so the chirality of catalyzing asymmetric reaction can be independently controlled, and the synthesis difficulty and cost of the chiral catalyst are greatly reduced; the catalyst can be used for catalyzing asymmetric transfer hydrogenation of aryl-aryl substituted ketone compounds, heterocyclic aromatic-aryl substituted ketone compounds and heterocyclic aromatic-heterocyclic aryl substituted ketone compounds, preparing chiral secondary alcohol compounds and achieving kinetic resolution of racemic alpha-allyl alcohol compounds.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a type of single chiral center catalyst and a method for preparing and catalyzing the synthesis of chiral alcohol compounds and chiral α-allyl alcohol. Background technique [0002] Chiral compounds play an important role in the pharmaceutical and material synthesis industries, especially in the field of medicine. Nearly half of the drugs are chiral, and more than 2 / 3 of the new drugs developed are chiral drugs. Chiral secondary alcohols are the most important class of chiral compounds and key intermediates for the synthesis of many other chiral compounds. They have a wide range of applications in both academia and industry. Electrically similar secondary alcohols, such as aryl-aryl-substituted, heteroaryl-aryl-substituted, and heteroaryl-heteroaryl-substituted chiral secondary alcohol compounds, have important applications in the field of new medicines . Although chemists have...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24B01J31/18C07F15/00C07D213/30C07D213/64C07D213/61C07D213/65C07D401/06
Inventor 邢祥友潘玉鹏尤义鹏陈福民何东旭金明宇陶冠宇
Owner SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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