Formation of vicinal secondary and all-carbon quaternary stereocenters in enantioenriched diazenes via branched-selective Pd-catalyzed allylic alkylation

Abstract

The synthesis of enantioenriched alkyl diazenes with vicinal secondary and all‑carbon quaternary stereocenters via palladium-catalyzed allylic alkylation is reported. Diazenes were formed in high diastereoselectivity and modest enantioselectivity. Notably, the ratio of branched to linear products was very high, a rarely observed phenomenon in palladium catalysis. The utility of this approach was demonstrated by cleaving the NN bond to form an α-secondary amine with a vicinal all‑carbon quaternary stereocenter.