Understanding mechanism driven regioselectivity in zirconium-catalysed hydroaminoalkylation: homoallylic amines from conjugated dienes.

The unexpected 4,1-hydroaminoalkylation of dienes provides selective access to linear homoallylic amines by zirconium catalysis. This switch from the traditional branched preferred regioselectivity to selective linear product formation using this early transition metal can be attributed to π-allyl intermediates. The reactivity of these isolated intermediates on a sterically accessible and coordinatively flexible chelating bis(ureate) Zr(iv) complex confirmed reversible C-C bond formation in hydroaminoalkylation catalysis.