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

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 RhI‐complex exhibits an extraordinarily high degree of tolerance to the va...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-03, Vol.62 (10), p.e202216799-n/a
Main Authors: Zhang, Junyou, Xu, Weici, Xu, Ming‐Hua
Format: Article
Language:English
Subjects:
Aromatic compounds
Asymmetric Cyclopropanation
Asymmetry
Catalysts
Chiral Diene
Coordination
Cyclopropane
Enantiomers
Metal Carbene
Organic compounds
penta-Substituted Cyclopropanes
Rhodium
Substitution reactions
Substrates
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 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 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 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. A simple, broad‐scope rhodium (I)/chiral diene catalytic system has been developed that allows otherwise difficult‐to‐access penta‐substituted cyclopropanes to be prepared in a highly enantioselective manner through asymmetric intramolecular cyclopropanation of rather challenging tri‐substituted allylic diazoacetates. Extraordinary high performance of RhI/diene complex is showcased with low catalyst loading as little as 0.1 mol %.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202216799