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A method for the efficient synthesis of optically active 2-pyrroline compounds catalyzed by an asymmetric organophosphine

A technology for pyrrolines and compounds, which is applied in the fields of organic chemistry, organic chemistry, bulk chemical production, etc. It can solve the problems of poor enantioselectivity and the development of synthetic methods for multi-substituted 2-pyrrolines, etc. Low cost, good industrial application prospect, high yield effect

Active Publication Date: 2020-06-30
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

With the help of a new chiral phosphine catalyst, He Zhengjie et al. developed the cyclization reaction of MBH carbonate and α, β-unsaturated imine with high enantioselectivity and diastereoselectivity [1+4], α , the substituents on the nitrogen atom of the β-unsaturated imine have a great influence on the stereoselectivity of the phosphine-mediated cyclization, replacing 4-nitrobenzenesulfonyl with other groups (tosyl, benzenesulfonyl) Acyl groups lead to poor enantioselectivity
[0006] Therefore, the synthetic method of enantioselective synthesis of multi-substituted 2-pyrrolines remains to be developed

Method used

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  • A method for the efficient synthesis of optically active 2-pyrroline compounds catalyzed by an asymmetric organophosphine
  • A method for the efficient synthesis of optically active 2-pyrroline compounds catalyzed by an asymmetric organophosphine
  • A method for the efficient synthesis of optically active 2-pyrroline compounds catalyzed by an asymmetric organophosphine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] In a sealed tube under nitrogen atmosphere, Compound 1a (0.25mmol), Compound 2a (0.30mmol), Catalyst I (10mol%) were dissolved in CH 2 Cl 2 (2.0 mL) was stirred at 25 °C for 48 h. After removal of the solvent, the crude residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate) to give the corresponding product 3aa.

[0035]

[0036] Yield 46%, dr>20:1, 88% ee.

[0037] White solid, mp 102.4-105.1°C. 1 H NMR (500Hz, CDCl 3 ): δ(ppm)7.71-7.68(m,2H),7.44-7.42(m,3H),7.31(d,J=8.0Hz,2H),7.12-6.99(m,5H),6.71(d,J =7.2Hz,2H),6.51(s,1H),6.28(s,1H),5.28(d,J=3.6Hz,1H),5.01(d,J=2.8Hz,1H),4.07-3.95(m ,2H),3.62(t,J=3.4Hz,1H),2.40(s,3H),2.02-1.92(m,1H),0.95(d,J=6.8Hz,3H),0.94(d,J= 6.8Hz, 3H). 13 C NMR (100Hz, CDCl 3 ): δ (ppm) 165.8, 144.9, 143.9, 142.2, 141.1, 133.6, 132.7, 129.6, 129.1, 128.5, 128.2, 128.0, 127.9, 127.4, 126.3, 125.3, 116.1, 71.1, 69.7, 53.5, 2 19.2, 19.1. HRMS: Accurate mass calculation [M+H] + (C 30 h 32 NO 4 S) is m / z...

Embodiment 2

[0039] In a sealed tube under nitrogen atmosphere, Compound 1a (0.25 mmol), Compound 2a (0.30 mmol), Catalyst II (10 mol%) were dissolved in CH 2 Cl 2 (2.0 mL) was stirred at 25 °C for 48 h. After removal of the solvent, the crude residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate) to give the corresponding product 3aa.

[0040]

[0041] Yield 6%, dr>20:1, 86% ee.

Embodiment 3

[0043] In a sealed tube under nitrogen atmosphere, Compound 1a (0.25 mmol), Compound 2a (0.30 mmol), Catalyst III (10 mol%) were dissolved in CH 2 Cl 2 (2.0 mL) was stirred at 25 °C for 48 h. After removal of the solvent, the crude residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate) to give the corresponding product 3aa.

[0044]

[0045] Yield 5%, dr>20:1, 67% ee.

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Abstract

The invention belongs to the field of an organic synthesis method, and discloses a method for efficiently synthesizing optically active 2-pyrroline compound through asymmetric organic phosphine catalyzing. The method is characterized by taking a chiral phosphine compound as a catalyst and enabling a compound as shown in a formula A which is shown in the description to react with a compound as shown in a formula B which is shown in the description, thus obtaining a compound as shown in a formula C which is shown in the description, wherein Ar<1> is selected from phenyl or substituted phenyl, Ar<2> is selected from phenyl or substituted phenyl, R<1> is selected from a sulfonyl protecting group, and R<2> is selected from alkyl or benzyl. The method disclosed by the invention is good in catalytic effect, a series of optically active polysubstituted 2-pyrroline can be obtained through enantioselective [1+4] cyclization of phosphine mediated MBH carbonate and alpha, beta-unsaturated imine, the yield is high, the stereoselectivity is good, the catalytic efficiency is good, the application range of a substrate is wide, the operation is simple, the cost is low, and a very good industrial application prospect is obtained.

Description

technical field [0001] The invention belongs to the field of organic synthesis methods, in particular to a method for efficiently synthesizing optically active 2-pyrroline compounds by asymmetric organophosphine catalysis. Background technique [0002] Chiral pyrroline and its derivatives are of great significance in natural products, drugs and enantioselective catalysis, and researchers are committed to developing asymmetric synthesis methods for pyrroline compounds. [0003] Organophosphine-catalyzed enantioselective cyclizations are an efficient synthetic strategy, for example, organophosphine-mediated asymmetric [3+2] cyclizations of imines or alkynoates with imines can yield optically active 3 -Pyrroline compounds, however, the synthesis of chiral pyrrolines by asymmetric catalytic [1+4] cyclization has not been reported yet. [0004] In 2015, Gregory C.Fu et al. used chiral spirocyclic phosphine to catalyze the enantioselective [1+4] cyclization of cyclic sulfonamides...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D207/48
CPCC07B2200/07C07D207/48Y02P20/55
Inventor 李鹏飞钱辰骁张庞淼淼
Owner SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA