title: Chemoselective Catalytic Oxidation of 1,2-Diols to α-Hydroxy Acids Controlled by TEMPO-ClO2 Charge-Transfer Complex.
abstract: Chemoselective catalytic oxidation from 1,2-diols to α-hydroxy acids in a cat. TEMPO/cat. NaOCl/NaClO2 system has been achieved. The use of a two-phase condition consisting of hydrophobic toluene and water suppresses the concomitant oxidative cleavage. A study of the mechanism suggests that the observed selectivity is derived from the precise solubility control of diols and hydroxy acids as well as the active species of TEMPO. Although the oxoammonium species TEMPO(+)Cl(-) is hydrophilic, the active species dissolves into the organic layer by the formation of the charge-transfer (CT) complex TEMPO-ClO2 under the reaction conditions.
authors.affiliation: Department of Basic Medicinal Sciences, Graduate School of Pharmaceutical Sciences, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8601, Japan.
authors.forename: Keisuke
authors.initials: K
authors.lastname: Furukawa
authors.affiliation: Department of Basic Medicinal Sciences, Graduate School of Pharmaceutical Sciences, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8601, Japan.
authors.forename: Masatoshi
authors.initials: M
authors.lastname: Shibuya
authors.affiliation: Department of Basic Medicinal Sciences, Graduate School of Pharmaceutical Sciences, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8601, Japan.
authors.forename: Yoshihiko
authors.initials: Y
authors.lastname: Yamamoto
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002384:Catalysis; D003497:Cyclic N-Oxides / Q000737:chemistry*; D006880:Hydroxy Acids / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D000438:Alcohols; D003497:Cyclic N-Oxides; D006880:Hydroxy Acids; C003959:TEMPO