Low Coordination State Rh-I-Complex as High Performance Catalyst for Asymmetric Intramolecular Cyclopropanation: Construction of penta-Substituted Cyclopropanes

Zhang, Junyou1,2,3; Xu, Weici2,3; Xu, Ming-Hua2,3,4

2023

10.1002/anie.202216799

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Impact Factor & Quartile

1433-7851

1521-3773

A simple, broad-scope rhodium(I)/chiral diene catalytic system for challenging asymmetric intramolecular cyclopropanation of various tri-substituted allylic diazoacetates was successfully developed. The low coordination state Rh-I-complex exhibits an extraordinarily high degree of tolerance to the variation in the extent of substitution of the allyl double bond, thus allowing the efficient construction of a wide range of penta-substituted, fused-ring cyclopropanes bearing three contiguous stereogenic centers, including two quaternary carbon stereocenters, in a highly enantioselective manner with ease at catalyst loading as low as 0.1 mol %. The stereoinduction mode of this Rh-I-carbene-directed asymmetric intramolecular cyclopropanation was investigated by DFT calculations, indicating that pi-pi stacking interactions between the aromatic rings of chiral diene ligand and diazo substrate play a key role in the control of the reaction enantioselectivity.

Asymmetric Cyclopropanation Chiral Diene Metal Carbene penta-Substituted Cyclopropanes Rhodium

SCI

English

NI Journal Papers

Corresponding

National Natural Science Foundation of China["21971103","21672229"] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Shenzhen Science and Technology Innovation Commission[JCYJ20200109141408054]

Chemistry

Chemistry, Multidisciplinary

WOS:000919861900001

WILEY-V C H VERLAG GMBH

CHEMISTRY

2-s2.0-85146650163

Web of Science

1.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150001, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
4.Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China

Zhang, Junyou,Xu, Weici,Xu, Ming-Hua. Low Coordination State Rh-I-Complex as High Performance Catalyst for Asymmetric Intramolecular Cyclopropanation: Construction of penta-Substituted Cyclopropanes[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2023,62(10).

Zhang, Junyou,Xu, Weici,&Xu, Ming-Hua.(2023).Low Coordination State Rh-I-Complex as High Performance Catalyst for Asymmetric Intramolecular Cyclopropanation: Construction of penta-Substituted Cyclopropanes.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,62(10).

Zhang, Junyou,et al."Low Coordination State Rh-I-Complex as High Performance Catalyst for Asymmetric Intramolecular Cyclopropanation: Construction of penta-Substituted Cyclopropanes".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 62.10(2023).