Abstract

Branched chiral allylic amines are useful building blocks and the aza-Claisen rearrangement (aCR) allows their synthesis from readily available allylic alcohols. The C,N-ligand (FIP-Cl) developed by Peters and coworkers makes the catalyst exceptionally active. Thus, loadings as low as 0.05 mol% in Pd can be used. Although many enantioselective reactions have been reported, they usually require ˜10 mol% Pd loadings. Importantly, the reaction can generate N-substituted quaternary centers with excellent ee (i.e. 5f: 98% ee).

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