Three-Component Gallium(III)-Promoted Addition of Halide Anions and Acetylenes to Donor-Acceptor Cyclopropanes

Roman A Novikov; Denis D Borisov; Anna V Tarasova; Yaroslav V Tkachev; Yury V Tomilov

doi:10.1002/anie.201803541

Three-Component Gallium(III)-Promoted Addition of Halide Anions and Acetylenes to Donor-Acceptor Cyclopropanes

Angew Chem Int Ed Engl. 2018 Aug 6;57(32):10293-10298. doi: 10.1002/anie.201803541. Epub 2018 Jul 17.

Authors

Roman A Novikov^{1

2}, Denis D Borisov¹, Anna V Tarasova¹, Yaroslav V Tkachev², Yury V Tomilov¹

Affiliations

¹ N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation.
² Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, 32 Vavilov st., 119991, Moscow, Russian Federation.

PMID: 29897640
DOI: 10.1002/anie.201803541

Abstract

A new strategy for the three-component addition of halide anions and acetylenes to donor-acceptor cyclopropanes (DACs) is presented. This reaction, which occurs with high E selectivity, is promoted by gallium(III) salts and based on the 1,2-zwitterionic reactivity of DACs. It opens up a new group of processes involving DACs. The reaction occurs readily with a broad range of substrates and is tolerant of various functional groups. This methodology makes it possible to assemble highly functionalized vinyl halides, which are very convenient building blocks in organic synthesis. A possible mechanism of this reaction and its stereochemical aspects are discussed in detail.

Keywords: alkynes; donor-acceptor cyclopropanes; gallium halides; trans addition; vinyl halides.