New protocol for allylic substitution with aryl and alkenyl copper reagents derived from organolithiums

Substitution of allylic picolinoates with copper reagents derived from sp2-carbon-lithiums and CuBr·Me2S was established to furnish anti SN2′ products with almost perfect regioselectivity and chirality transfer. The preparations of organolithiums such as lithium–halogen exchange and ortho lithiation were coupled to the substitution to install various sp2-carbon groups, which include Ph, 2,6-Me2C6H3, 4-Me-2,6-(MOMO)C6H2, and cis and trans 1-heptenyl groups.