Letters in Organic Chemistry [ Investigation of the Aqueous Transmetalation of π-Allylpalladium with Indium: Some Theoretical and Experimental Evidence About the Nature of Allylindium Intermediates ]

In this paper we report some theoretical and experimental evidence concerning the nature of the allyl-In intermediate generated by umpolung of allyl-Pd complexes in the Pd(OAc)2/TPPTS catalysed allylation reaction of benzaldehyde. The allylic substrate reacts at the substituted terminus, because of the formation of an equilibrating mixture of η1-allyl-In(I) specie with the γ-substituted regioisomer being more reactive.