Fluorotrifluoromethyl Group Installation: Tetrasubstituted Tertiary Stereocenters Containing C-F and C-CF 3 Bonds via Copper-Mediated Allylic Substitution.

Tetrasubstituted tertiary centers containing a fluorotrifluoromethyl (FTF) motif were obtained from secondary 3-fluoro-3-trifluoromethyl allylic phosphates by a copper(I)-mediated allylic substitution reaction using Grignard reagents. The reaction features a broad substrate scope, high γ-regioselectivity, and excellent ( E )-stereoselectivity. Two examples of chirality transfer from enantiopure secondary fluorine-substituted allylic phosphates to the corresponding scalemic products indicate the stereoselective potential of the method to install FTF stereocenters.