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 sp³-sp³ C-C bonds directly from C-H bonds. A wide range of aromatic and heteroaromatic linear (E)-α-nitro-arylpentenoates are obtained as single olefin isomers in excellent yields directly from terminal olefin substrates and methyl nitroacetate. The use of DMSO as a π-acidic ligand was found to be crucial for promoting functionalization of the π-allylPd intermediate. Products from this reaction are valuable synthetic intermediates and are readily transformed to amino esters via selective reduction and optically enriched α,α-disubstituted amino acid precursors via asymmetric conjugate addition.