Journal of the American Chemical Society, Vol.139, No.32, 11044-11047, 2017
Method for Highly Enantioselective Ligation of Two Chiral C(sp(3)) Stereocenters
A method is described for the joining of two alpha-lithiated C(sp(3)) stereocenters efficiently and with retention of configuration. The key step involves the effective removal of two electrons from a chiral organocuprate R2CuLi, by i-propyl 2,4-dinitrobenzoate to form a Cu(III) complex that undergoes at -90 degrees C accelerated reductive elimination enantioselectively and exclusively without the formation of free radicals.