Asymmetric Ni-Catalyzed Conjugate Allylation of Activated Enones

2008-04-09T00:00:00Z (GMT) by Joshua D. Sieber James P. Morken
The nickel-catalyzed enantioselective addition of allylboronic acid pinacol ester, allylB(pin), is described. This reaction is highly effective with dialkylidene ketones and favors the allylation of the benzylidene site in nonsymmetric substrates. The reaction appears to proceed by conversion of the dialkylidene ketone substrate to an unsaturated π-allyl complex (<b>I</b>), followed by reductive elimination. Enantioselectivities range from 91 to 94% ee for a range of substrates when chiral ligand <b>14</b> is employed.