Combined Effect of Palladium Catalyst and the Alcohol to Promote the Uncommon Bis‐Alkoxycarbonylation of Allylic Substrates

A chemoselective method for the carbonylation of allylic substrates CH2=CHCH2X (X=OAc, OC(O)CH2CN, OPh, OEt, OC(O)OPh, OC(O)OiBu, N(H)C(O)Ph, N(Ph)C(O)Ph, N(H)Boc, N(Ph)Boc, Ph, CO2Bn, CN), leading to alkyl succinates with preservation X group, under Pd(II)-catalyzed oxidative conditions, has been developed. Our shows a completely different inverse chemoselectivity respect “classical” substitutive allyl compounds, which is known provide β,γ-unsaturated carbonyl derivatives through formation π-allylpalladium intermediate. An accurate study, carried out using acetate as model substrate, allowed maximize selectivity in envisioned 2-CH2X substituted succinates. The best catalyst generated situ by mixing Pd(TFA)2 (TFA=trifluoroacetate) and N,N′-di(anthracen-9-yl)butane-2,3-diimine ligand. p-Benzoquinone was used oxidant presence benzyl alcohol, acts nucleophile solvent, 4 bar CO at 20 °C. combined effect ligand nucleophile, rationalized DFT calculations, observed both promoting bis-alkoxycarbonylation process preventing π-allylpalladium-mediated side reactions, allowing attainment succinate moderate good yields.