Preparation and Reactivity of Acyclic Chiral Allylzinc Species by a Zinc-Brook Rearrangement

Angew Chem Int Ed Engl. 2016 May 10;55(20):6057-61. doi: 10.1002/anie.201602393. Epub 2016 Apr 9.

Abstract

The zinc-Brook rearrangement of enantiomerically enriched α-hydroxy allylsilane produces a chiral allylzinc intermediate, which reacts with retention of configuration in the presence of an electrophile. Two remarkable features of this transformation are the stereochemical outcome during the formation of the allylzinc species and the complete stereocontrol in the organized six-membered transition state, which leads to an overall and complete transfer of chirality within the reaction sequence.

Keywords: Brook rearrangement; allylic compounds; chirality; olefins; zinc.

Publication types

  • Research Support, Non-U.S. Gov't