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Efficient Oxidation of 1,2‐Diols into α‐Hydroxyketones Catalyzed by Organotin Compounds
Author(s) -
Maki Toshihide,
Iikawa Shinya,
Mogami Gen,
Harasawa Hitomi,
Matsumura Yoshihiro,
Onomura Osamu
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200900159
Subject(s) - chemistry , catalysis , bromide , tin , electrochemistry , diol , medicinal chemistry , stereoselectivity , organic chemistry , bond cleavage , electrode
Get selective! A selective oxidation of 1,2‐diols to α‐hydroxyketones catalyzed by organotin compounds has been developed (see scheme). Invaluable chemo‐ and stereoselectivity were found in the reaction. The catalytic system has been achieved by electrochemical and chemical oxidation.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 α‐hydroxyketones in good to excellent yields without CC 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.