Nucleophilic addition to ir-allylpalladium complexes regioselectivity

Regioselectivity in the Addition of Soft Carbon Nucleophiles to ir-Allylpalladium Complexes 627... 

Addition of MeMgl158 or PhLi160 to ir-allylpalladium complexes derived from methylenenoibomane exhibits selective C—C bond formation at die more hindered allyl terminus. Soft carbon nucleophiles with the same allyl species show the opposite regioselectivity (equation 252).158,160... 

All of the various sulfur nucleophiles that have been studied, including PhSCh—, RS— and (Et0)2P(0)S—, have been demonstrated to add to ir-allylpalladium complexes by ligand addition. Interpretation of the regioselectivities of these nucleophiles must be tempered by the realization that the allyl— SChPh, -SR and -SP(0)(0Et)2 products are capable of isomerization by means of reentering the ir-allylpalladium manifold. 

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