A quinone-mediated general synthetic platform for the construction of primary a-tertiary amines from
abundant primary a-branched amine starting materials is described. This procedure pivots on the
efficient in situ generation of reactive ketimine intermediates and subsequent reaction with carboncentered nucleophiles such as organomagnesium and organolithium reagents, and TMSCN, creating
quaternary centers. Furthermore, extension to reverse polarity photoredox catalysis enables reactivity
with electrophiles, via a nucleophilic a-amino radical intermediate. This efficient, broadly applicable and
scalable amine-to-amine synthetic platform was successfully applied to library and API synthesis and in
the functionalization of drug molecules
