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

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

Olivieri, Diego;Spadoni, Gilberto;
2022

Abstract

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 of the X group, under Pd(II)-catalyzed oxidative carbonylation conditions, has been developed. Our method shows a completely different inverse chemoselectivity with respect to the “classical” substitutive carbonylation of the allyl compounds, which is known to provide β,γ-unsaturated carbonyl derivatives through the formation of a π-allylpalladium intermediate. An accurate study, carried out using allyl acetate as model substrate, allowed to maximize the selectivity in the envisioned 2-CH2X substituted succinates. The best catalyst is generated in situ by mixing Pd(TFA)2 (TFA=trifluoroacetate) and the N,N′-di(anthracen-9-yl)butane-2,3-diimine ligand. p-Benzoquinone was used as oxidant in presence of benzyl alcohol, which acts as a nucleophile and as a solvent, under 4 bar of CO at 20 °C. A combined effect of the ligand and the nucleophile, rationalized through DFT calculations, has been observed both in promoting the bis-alkoxycarbonylation process and in preventing π-allylpalladium-mediated side reactions, allowing the attainment of succinate derivatives with moderate to good yields.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11576/2695431
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