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| - A Joint Experimental and Theoretical Study of thePalladium-Catalyzed Electrophilic Allylation of Aldehydes
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| - Palladium-catalyzed electrophilic allylation of aldehydes with allylstannanes has been proposed in theliterature as a model reaction illustrating the potential of nucleophilic η1-allyl palladium pincer complexesto promote new catalytic processes. This reaction was studied by a joint experimental and theoreticalapproach. It was shown that pincer palladium complexes featuring a S∼P∼S and a S∼C∼S tridentateligand are efficient catalysts for this reaction. The full mechanism of this transformation was studied indetail by means of DFT calculations. Two pathways were explored: the commonly proposed mechanisminvolving η1-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 mildconditions. The mechanism involving an η1-allyl palladium intermediate has been discarded on energeticgrounds, the nucleophilic attack and the transmetalation step being more energetically demanding thanthe direct reaction between allyltin and the aldehyde. On the other hand, a mechanism where the palladiumacts as a Lewis acid proved to be fully consistent with all experimental and theoretical results. Thismechanism involves (L∼X∼L)Pd+ species which activate the aldehyde moiety toward nucleophilic attack.
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