Chiral Phosphoric Acid Catalyzed Conversion of Epoxides into Thiiranes: Mechanism, Stereochemical Model, and New Catalyst Design

Duan, Meng1,2,3,5,6; Diaz-Oviedo, Christian David4; Zhou, Yang5,6; Chen, Xiangyang3; Yu, Peiyuan5,6; List, Benjamin4; Houk, Kendall N.3; Lan, Yu1,2

2022

10.1002/anie.202113204

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

Computations and experiments leading to new chiral phosphoric acids (CPAs) for epoxide thionations are reported. Density functional theory calculations reveal the mechanism and origin of the enantioselectivity of such CPA-catalyzed epoxide thionations. The calculated mechanistic information was used to design new efficient CPAs that were tested experimentally and found to be highly effective. Bulky ortho-substituents on the 3,3 '-aryl groups of the CPA are important to restrict the position of the epoxide in the key transition states for the enantioselectivity-determining step. Larger para-substituents significantly improve the enantioselectivity of the reaction.

Catalyst Design Chiral Phosphoric Acids DFT Calculations Organocatalysis Stereochemical Model

SCI ; EI

英语

NI论文 ; ESI高被引

其他

National Natural Science Foundation of China[21822303,21772020] ; National Science Foundation["CHE-1764328","OCI-1053575"] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000742557900001

WILEY-V C H VERLAG GMBH

20220311476901

Catalysis ; Density functional theory ; Enantioselectivity

Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

CHEMISTRY

Web of Science

1.Zhengzhou Univ, Green Catalysis Ctr, Zhengzhou 450001, Henan, Peoples R China
2.Zhengzhou Univ, Coll Chem, Zhengzhou 450001, Henan, Peoples R China
3.Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
4.Max Planck Inst Kohlenforsch, D-45470 Mulheim, Germany
5.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Dept Chem, Shenzhen 518055, Peoples R China
6.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China

Duan, Meng,Diaz-Oviedo, Christian David,Zhou, Yang,et al. Chiral Phosphoric Acid Catalyzed Conversion of Epoxides into Thiiranes: Mechanism, Stereochemical Model, and New Catalyst Design[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2022,61(9).

Duan, Meng.,Diaz-Oviedo, Christian David.,Zhou, Yang.,Chen, Xiangyang.,Yu, Peiyuan.,...&Lan, Yu.(2022).Chiral Phosphoric Acid Catalyzed Conversion of Epoxides into Thiiranes: Mechanism, Stereochemical Model, and New Catalyst Design.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,61(9).

Duan, Meng,et al."Chiral Phosphoric Acid Catalyzed Conversion of Epoxides into Thiiranes: Mechanism, Stereochemical Model, and New Catalyst Design".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61.9(2022).