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Catalytic Asymmetric Allylic Substitution with Copper(I) Homoenolates Generated from Cyclopropanols

Authors :
Si-Wei Zhou
Liang Yin
Chang-Yun Shi
Qi Zhang
Source :
Angewandte Chemie International Edition. 60:26351-26356
Publication Year :
2021
Publisher :
Wiley, 2021.

Abstract

By using copper(I) homoenolates as nucleophiles, which are generated through the ring-opening of 1-substituted cyclopropane-1-ols, a catalytic asymmetric allylic substitution with allyl phosphates is achieved in high to excellent yields with high enantioselectivity. Both 1-substituted cyclopropane-1-ols and allylic phosphates enjoy broad substrate scopes. Remarkably, various functional groups, such as ether, ester, tosylate, imide, alcohol, nitro, and carbamate are well tolerated. Moreover, the present method is nicely extended to the asymmetric construction of quaternary carbon centers. Some control experiments argue against a radical-based reaction mechanism and a catalytic cycle based on a two-electron process is proposed. Finally, the synthetic utilities of the product are showcased by means of the transformations of the terminal olefin group and the ketone group.

Details

ISSN :
15213773 and 14337851
Volume :
60
Database :
OpenAIRE
Journal :
Angewandte Chemie International Edition
Accession number :
edsair.doi.dedup.....3b3e3e7b71923baf0aaa3b8128ba2b7e
Full Text :
https://doi.org/10.1002/anie.202110709