Phosphine-Catalyzed Activation of Vinylcyclopropanes: Rearrangement of Vinylcyclopropylketones to Cycloheptenones

Jun Wu; Yuhai Tang; Wen Wei; Yong Wu; Yang Li; Junjie Zhang; Yuansuo Zheng; Silong Xu

doi:10.1002/anie.201800555

Phosphine-Catalyzed Activation of Vinylcyclopropanes: Rearrangement of Vinylcyclopropylketones to Cycloheptenones

Angew Chem Int Ed Engl. 2018 May 22;57(21):6284-6288. doi: 10.1002/anie.201800555. Epub 2018 May 2.

Authors

Jun Wu¹, Yuhai Tang¹, Wen Wei¹, Yong Wu¹, Yang Li¹, Junjie Zhang¹, Yuansuo Zheng¹, Silong Xu¹

Affiliation

¹ Department of Chemistry, School of Science, Xi'an Key Laboratory of Sustainable Energy Materials Chemistry, Xi'an Jiaotong University, Xi'an, 710049, P. R. China.

PMID: 29645401
DOI: 10.1002/anie.201800555

Abstract

We report a phosphine-catalyzed activation of electron-deficient vinylcyclopropanes (VCPs) to generate an ambident C₅ synthon that is poised to undergo consecutive reactions. The utility of the activation is demonstrated in a phosphine-catalyzed rearrangement of vinylcyclopropylketones to cycloheptenones in good yields with a broad substrate scope. Mechanistic investigations support a stepwise process comprising homoconjugate addition, water-assisted proton transfer, and 7-endo-trig S_N 2' ring closure.

Keywords: cycloheptenones; organocatalysis; phosphine catalysis; rearrangement; vinylcyclopropanes.

Publication types

Research Support, Non-U.S. Gov't