Efficient oxidation of 1,2-diols into alpha-hydroxyketones catalyzed by organotin compounds.
Electrochemical oxidation of 1,2-diols with a catalytic amount of an organotin compound and a bromide ion as mediators has been developed. Various cyclic and acyclic 1,2-diols were oxidized into the corresponding alpha-hydroxyketones in good to excellent yields without C-C bond cleavage. Also, oxidation with the use of chemical oxidants was accomplished in the presence of a catalytic amount of an organotin compound. These reactions could discriminate 1,2-diols from isolated hydoxyl groups or 1,3-diols. In the case of a conformationally restricted cyclic 1,2-diol, the axial hydroxyl group was oxidized exclusively. Mono-, di-, and trialkylated tin compounds were examined as mediators and dialkylated tin compounds showed higher catalytic activity than mono- and trisubstituted ones. Me(2)SnCl(2) was found to be the most suitable mediator for the selective oxidation.
Maki
Toshihide
T
Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan.
Iikawa
Shinya
S
Mogami
Gen
G
Harasawa
Hitomi
H
Matsumura
Yoshihiro
Y
Onomura
Osamu
O
D000438:Alcohols / Q000737:chemistry*; D000478:Alkylation; D001965:Bromides / Q000737:chemistry; D002384:Catalysis; D002851:Chromatography, High Pressure Liquid; D007659:Ketones / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009947:Organotin Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
D000438:Alcohols; D001965:Bromides; D007659:Ketones; D009947:Organotin Compounds