Lewis Acid-Promoted Oxidative Addition of Thioimidates to Pd(0)

The isomeric S-methyldihydropyrrins 9-Z and 9-E exhibit markedly different behavior in Pd(0)-catalyzed cross-coupling reactions. Thioimidates 9-Z are readily converted to imines 10-Z employing Pd(0)/AlkZnI. Under identical conditions 9-E are inert. Oxidative addition to Pd(0) requires activation by Zn or other Lewis acids, which is sterically unfavorable with 9-E. Analogous results were obtained with the related thioimidates 11-E,Z as well as with methylthiopyridines 19α−γ. In the case of both 11 and 19 oxidative addition to Pd(0) was greatly facilitated in the presence of BF₃·Et₂O. The importance of Lewis acid activation to Pd(0) oxidative addition in such substrates appears to be a general phenomenon not previously recognized.