Low Coordination State RhI‐Complex as High Performance Catalyst for Asymmetric Intramolecular Cyclopropanation: Construction ofpenta‐Substituted Cyclopropanes

Author:

Zhang Junyou12,Xu Weici2,Xu Ming‐Hua23ORCID

Affiliation:

1. School of Chemistry and Chemical Engineering Harbin Institute of Technology Harbin 150001 China

2. Shenzhen Grubbs Institute and Department of Chemistry Guangdong Provincial Key Laboratory of Catalysis Southern University of Science and Technology Shenzhen 518055 China

3. School of Chemistry and Chemical Engineering Henan Normal University Xinxiang Henan 453007 China

Abstract

AbstractA simple, broad‐scope rhodium(I)/chiral diene catalytic system for challenging asymmetric intramolecular cyclopropanation of varioustri‐substituted allylic diazoacetates was successfully developed. The low coordination state RhI‐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 ofpenta‐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 RhI‐carbene‐directed asymmetric intramolecular cyclopropanation was investigated by DFT calculations, indicating that π‐π stacking interactions between the aromatic rings of chiral diene ligand and diazo substrate play a key role in the control of the reaction enantioselectivity.

Funder

National Natural Science Foundation of China

Guangdong Provincial Key Laboratory Of Catalysis

Science, Technology and Innovation Commission of Shenzhen Municipality

Publisher

Wiley

Subject

General Chemistry,Catalysis

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