TY - JOUR T1 - Palladium-catalyzed deracemization of allylic carbonates in water with formation of allylic alcohols: hydrogen carbonate ion as nucleophile in the palladium-catalyzed allylic substitution and kinetic resolution. AU - Lüssem,Bernhard J, AU - Gais,Hans-Joachim, PY - 2003/6/6/pubmed PY - 2003/6/6/medline PY - 2003/6/6/entrez SP - 6066 EP - 7 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 125 IS - 20 N2 - The palladium-catalyzed deracemization of racemic cyclic and acyclic allylic methyl carbonates in water in the presence of N,N'-(1R,2R)-1,2-cyclohexanediylbis[2-(diphenylphophino)benzamide] proceeds with high enantioselectivities to give the corresponding allylic alcohols in high yields. This deracemization involves a palladium-catalyzed allylic substitution with the in-situ-formed hydrogen carbonate ion and an irreversible decomposition of the intermediate allylic hydrogen carbonates, with formation of the corresponding allylic alcohols. The palladium-catalyzed reaction of racemic cyclic allylic acetates with potassium hydrogen carbonate in water in the presence of the chiral bisphosphane proceeds with a highly selective kinetic resolution to give the corresponding allylic alcohols and allylic acetates. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/12785831/Palladium_catalyzed_deracemization_of_allylic_carbonates_in_water_with_formation_of_allylic_alcohols:_hydrogen_carbonate_ion_as_nucleophile_in_the_palladium_catalyzed_allylic_substitution_and_kinetic_resolution_ DB - PRIME DP - Unbound Medicine ER -