Enantioselective biocatalytic desymmetrization for synthesis of enantiopure cis-3,4-disubstituted pyrrolidines

被引：14

作者：

Hu, Hui-Juan ^{[1
,2
]}

Wang, Qi-Qiang ^{[1
,3
]}

Wang, De-Xian ^{[1
,3
]}

Ao, Yu-Fei ^{[1
,3
]}

机构：

[1] Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, CAS Key Lab Mol Recognit & Funct, Beijing 100190, Peoples R China

[2] State Key Lab NBC Protect Civilian, Beijing 102205, Peoples R China

[3] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

来源：

GREEN SYNTHESIS AND CATALYSIS | 2021年 / 2卷 / 03期

基金：

中国国家自然科学基金;

关键词：

Biotransformation; Desymmetrization; Enantioselectivity; Amidase; Catalytic mechanism; KINETIC RESOLUTION; DESIGN; ACIDS; BIOTRANSFORMATIONS; CONSTRUCTION; EFFICIENT; NITRILES; POTENT;

D O I：

10.1016/j.gresc.2021.07.002

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A versatile biocatalytic desymmetric method for efficiently accessing enantiopure cis-3,4-disubstituted pyrrolidines was developed. Catalyzed by amidase-containing E. coli whole cells, a series of meso pyrrolidine-2,5-dicarboxamides were hydrolyzed to obtain 4-carbamoylpyrrolidine-3-carboxylic acid derivatives in 47%-95% yields and 62% similar to >99.5% ee values under mild condition. The catalytic efficiency and enantioselectivity are related to the substituents in the phenyl ring. The enzyme-substrate binding mode is established and the high enantioselectivity of amidase is revealed by MD simulations. The improvement of biocatalytic efficiency has been preliminarily explored through protein engineering.

引用

页码：324 / 327

页数：4

共 50 条

[21] Lewis acid mediated diastereoselective keto-ene cyclization on chiral perhydro-1,3-benzoxazines: synthesis of enantiopure cis-3,4-disubstituted 3-hydroxypyrrolidines
Andres, Celia
Gonzalez, Israel
Nieto, Javier
Roson, Carlos D.
TETRAHEDRON, 2009, 65 (47) : 9728 - 9736
[22] trans-3,4-disubstituted pyrrolidines by 1,3-dipolar cycloaddition:: enantioselective approaches and their limitations
Karlsson, S
Han, F
Högberg, HE
Caldirola, P
TETRAHEDRON-ASYMMETRY, 1999, 10 (13) : 2605 - 2616
[23] Successive Nucleophilic and Electrophilic Allylation for the Catalytic Enantioselective Synthesis of 2,4-Disubstituted Pyrrolidines
Luo, Guoshun
Xiang, Ming
Krische, Michael J.
ORGANIC LETTERS, 2019, 21 (08) : 2493 - 2497
[24] Generation, electrocyclic ring opening, and unprecedented conversion of a 3-acylaminoazetinone into cis-3,4-disubstituted azetidinones
Wolfe, S
Ro, S
Shi, Z
CANADIAN JOURNAL OF CHEMISTRY, 2001, 79 (08) : 1259 - 1271
[25] Asymmetric synthesis of 2,4-disubstituted pyrrolidines
Wang, Q
Sasaki, NA
Potier, P
TETRAHEDRON LETTERS, 1998, 39 (32) : 5755 - 5758
[26] Synthesis of enantiopure 3,4-disubstituted piperidines (vol 7, pg 1591, 1996)
Amat, M
Hidalgo, J
Bosch, J
TETRAHEDRON-ASYMMETRY, 1996, 7 (07) : 1845 - &
[27] Synthesis of trans/cis-3,4-Disubstituted 1,2,3,4-Tetrahydroisoquinolines by Nucleophilic Acyl Substitution of Homophthalic Anhydride with Aldimines
Hammad, Sherif F.
Smith, Forrest T.
JOURNAL OF HETEROCYCLIC CHEMISTRY, 2013, 50 (01) : 114 - 119
[28] SYN-ANTI SELECTIVITY IN CYCLOADDITIONS .2. REACTION OF CYCLIC NITRONES WITH CIS-3,4-DISUBSTITUTED CYCLOBUTENES
MICHELI, CD
GAMBAINVERNIZZI, A
GANDOLFI, R
TETRAHEDRON LETTERS, 1975, (29) : 2493 - 2496
[29] SYN-ANTI ISOMERISM IN THE REACTIONS OF CIS-3,4-DISUBSTITUTED CYCLOBUTENES .7. HF/3-21G TRANSITION STRUCTURES OF THE REACTION OF DIAZOMETHANE WITH CIS-3,4-DICHLOROCYCLOBUTENE
BAGATTI, M
ORI, A
RASTELLI, A
BURDISSO, M
GANDOLFI, R
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1992, (10): : 1657 - 1659
[30] Efficient and Highly Selective Synthesis of Enantiopure cis- or trans-3,4-Disubstituted 1,2,3,4-Tetrahydroisoquinolines
Concellon, Jose M.
Tuya, Paula
del Solar, Virginia
Garcia-Granda, Santiago
Rosario Diaz, M.
ORGANIC LETTERS, 2009, 11 (16) : 3750 - 3753

← 1 2 3 4 5 →