Stereoselective synthesis of tetrasubstituted olefins through a halogen-induced 1,2-silyl migration

Nicholas T Barczak; Douglas A Rooke; Zachary A Menard; Eric M Ferreira

doi:10.1002/anie.201303007

Stereoselective synthesis of tetrasubstituted olefins through a halogen-induced 1,2-silyl migration

Angew Chem Int Ed Engl. 2013 Jul 15;52(29):7579-82. doi: 10.1002/anie.201303007. Epub 2013 Jun 10.

Authors

Nicholas T Barczak¹, Douglas A Rooke, Zachary A Menard, Eric M Ferreira

Affiliation

¹ Department of Chemistry, Colorado State University, 1872 Campus Delivery, Fort Collins, CO 80523, USA.

PMID: 23754706
DOI: 10.1002/anie.201303007

Abstract

Migrating through Si valley: The highly stereoselective formation of α-silyl-β- haloenones by way of silicon group migration is described. Electrophilic activation of the alkyne by N-halosuccinimides induced an anti-selective migration to give highly substituted enones (see scheme). These enone products can be readily converted to the all-carbon tetrasubstituted alkenes while maintaining their geometry.

Keywords: alkene geometry; alkynes; halosilylation; migration; stereoselectivity.

Publication types

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

MeSH terms

Alkenes / chemical synthesis*
Alkenes / chemistry
Alkynes / chemistry
Halogens / chemistry*
Silicon / chemistry*
Stereoisomerism

Substances

Alkenes
Alkynes
Halogens
Silicon