A joint experimental and theoretical study of the palladium-catalyzed electrophilic allylation of aldehydes

作者：Piechaczyk Olivier; Cantat Thibault; Mezailles Nicolas; Le Floch Pascal^*

来源：Journal of Organic Chemistry, 2007, 72(11): 4228-4237.

DOI：10.1021/jo070467t

Palladium-catalyzed electrophilic allylation of aldehydes with allylstannanes has been proposed in the literature as a model reaction illustrating the potential of nucleophilic eta(1)-allyl palladium pincer complexes to promote new catalytic processes. This reaction was studied by a joint experimental and theoretical approach. It was shown that pincer palladium complexes featuring a S similar to P similar to S and a S similar to C similar to S tridentate ligand are efficient catalysts for this reaction. The full mechanism of this transformation was studied in detail by means of DFT calculations. Two pathways were explored: the commonly proposed mechanism involving eta(1)-allyl palladium intermediates and a Lewis acid promoted mechanism. Both of these mechanisms were compared to the direct transformation that was shown experimentally to occur under mild conditions. The mechanism involving an eta(1)-allyl palladium intermediate has been discarded on energetic grounds, the nucleophilic attack and the transmetalation step being more energetically demanding than the direct reaction between allyltin and the aldehyde. On the other hand, a mechanism where the palladium acts as a Lewis acid proved to be fully consistent with all experimental and theoretical results. This mechanism involves (L similar to X similar to L)Pd(+) species which activate the aldehyde moiety toward nucleophilic attack.

• 出版日期2007-5-25