title: Mechanism insight into the cyanide-catalyzed benzoin condensation: a density functional theory study.
abstract: The reaction mechanism of the cyanide-catalyzed benzoin condensation without protonic solvent assistance has been studied computationally for the first time employing the density functional theory (B3LYP) method in conjunction with 6-31+G(d,p) basis set. Four possible pathways have been investigated. A new proposed pathway on the basis of the Lapworth mechanism is determined to be the dominant pathway in aprotic solvent, in which the formation of the Lapworth's cyanohydrin intermediate is a sequence including three steps assisted by benzaldehyde, clearly manifesting that the reaction can take place in aprotic solvents such as DMSO. In this favorable pathway with six possible transition states located along the potential energy surface, the reaction of the cyanide/benzaldehyde complex with another benzaldehyde to afford an alpha-hydroxy ether is the rate-determining dynamically with the activation free energy barrier of 26.9 kcal/mol, and the step to form cyanohydrin intermediate from alpha-hydroxy ether is partially rate-determining for its relatively significant barrier 20.0 kcal/mol.
authors.affiliation: College of Chemistry, Key Lab of Green Chemistry and Technology in Ministry of Education and State Key Laboratory of Biotherapy, Sichuan University, Chengdu 610064, People's Republic of China.
authors.forename: Yunqing
authors.initials: Y
authors.lastname: He
authors.forename: Ying
authors.initials: Y
authors.lastname: Xue
mesh_terms: D001573:Benzoin / Q000737:chemistry*; D002384:Catalysis; D008958:Models, Molecular; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry*; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D009570:Nitriles; D012997:Solvents; D001573:Benzoin