Copper-Catalyzed Addition of Grignards to Allylic α-Haloacetates

Significance

The authors describe a copper-­catalyzed allylic substitution of allylic α-chloro­acetates 1. While this is the first allylic substitution on these electrophiles, similar substrate classes have also been examined by Trost and Alexakis. This transformation is an alternative strategy to the 1,4-addition of a Grignard reagent to an unsaturated aldehyde; a strategy often marred by competitive 1,2-addition and double additions.

Review: T. Jerphagnon, M. G. Pizzuti, A. J. Minnaard, B. L. Feringa Chem. Soc. Rev. 2009, 38, 1039-1075.