Iridium-Catalyzed Asymmetric Allylic Alkylation of Deconjugated Butyrolactams.

Compared with the ever-growing list of nonprochiral nucleophiles in Ir-catalyzed asymmetric allylic substitution reactions, prochiral nucleophiles are less studied. We present a new prochiral nucleophile, namely, deconjugated butyrolactam, for Ir-catalyzed asymmetric allylic alkylation (AAA). This reaction provides access to α-allyl deconjugated butyrolactams with a moderate to good dr and an excellent er. This is the first AAA reaction of deconjugated butyrolactams. Allyl transposition through Cope rearrangement appears to proceed stereospecifically to form γ-allyl conjugated butyrolactams.