[reaction: see text] The first asymmetric palladium-catalyzed conjugate addition of arylboronic acids to alpha,beta-unsaturated aldehydes, ketones, and esters is described. For cyclic substrates, excellent chemo-, regio-, and enantioselectivities are achieved when a Pd(O2CCF3)2/DuPHOS catalyst is applied.

For the first time, an excellent enantioselectivity has been obtained in the conjugate addition of hard organometallic reagents to alpha,beta-unsaturated lactams bearing appropriate protecting-activating groups on the nitrogen.

The complex formed from Pd(CH(3)CN)(4)(BF(4))(2) and (R,R)-MeDUPHOS is a highly enantioselective catalyst for the asymmetric conjugate addition of aryltriethylsiloxanes to a variety of unsaturated ketones, lactones and lactams.

No abstract