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

Qi Zhang; Si-Wei Zhou; Chang-Yun Shi; Liang Yin

doi:10.1002/anie.202110709

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

Angew Chem Int Ed Engl. 2021 Dec 6;60(50):26351-26356. doi: 10.1002/anie.202110709. Epub 2021 Nov 3.

Authors

Qi Zhang¹, Si-Wei Zhou¹, Chang-Yun Shi¹, Liang Yin¹

Affiliation

¹ CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.

PMID: 34617380
DOI: 10.1002/anie.202110709

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.

Keywords: allylic substitution; asymmetric catalysis; copper catalyst; cyclopropanols; homoenolates.