Catalytic Intermolecular Allylic C-H Alkylation

The first electrophilic Pd(II)-catalyzed allylic C-H alkylation is reported, providing a novel method for formation of sp(3)-sp(3) C-C bonds directly from C-H bonds. A wide range of aromatic and heteroaromatic linear (E)-alpha-nitro-arylpentenoates are obtained as single olefin isomers in excellent yields directly from terminal olefin substrates and methyl nitroacetate. Theuse of DMSO as a pi-acidic ligand was found to be crucial for promoting functionalization of the pi-allylPd intermediate. Products from this reaction are valuable synthetic intermediates and are readily transformed to amino esters via selective reduction and optically enriched alpha,alpha-disubstituted amino acid precursors via asymmetric conjugate addition.