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Synthesis 2009(20): 3449-3459  
DOI: 10.1055/s-0029-1216972
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Chemo- and Product-selective Electrooxidation of 3-(Arylthiomethyl)-Δ³-cephems

Hideo Tanaka*a, Yoshihisa Tokumarua,c, Ken-ichi Fukuia, Manabu Kuroboshia, Sigeru Toriia,d, Anny Jutandb, Christian Amatore*b
a Department of Applied Chemistry, Faculty of Engineering, Okayama University, Tsushima-naka 3-1-1, Okayama 700-8530, Japan
Fax: +81(86)2518079; e-Mail: tanaka95@cc.okayama-u.ac.jp;
b Ecole Normale Supérieure, Département de Chimie, UMA CNRS 8640, 24, Rue Lhomond, 75231 Paris Cedex 5, France
c Otsuka Chemical Co. Ltd., 463 Kagasuno, Kawauti-cho, Tokushima 771-0193, Japan
d The Institute of Creative Chemistry Co., Musa 874-5, Okayama 701-2141, Japan
Further Information

Publication History

Received 13 April 2009
Publication Date:
28 August 2009 (online)

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Abstract

Electrolysis of 3-arylthiomethyl-Δ³-cephems possessing various substituents on the arylthio moiety undergo chemoselective and product-selective electrooxidation to give several different products. These include isomeric mixtures of the corresponding methoxylated cephems, a bis[(Δ³-cephem-3-yl)methyl]disulfide or a 3-dimethoxymethyl-Δ³-cephem. The selectivity of the oxidation is highly dependent on the nature of the substituents on the arylthio moiety which suggests that both steric and electronic effects play an important role in the electrooxidation of 3-arylthiomethyl-Δ³-cephems.

Key words

antibiotics - chemoselective - electrooxidation - radical cation

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10

Isomerization of 3-exo-methylene-4-methoxycepham 3c into 3-methoxymethyl-Δ³-cephem 3a was accomplished in MeOH containing HCl.8

11

Tanaka, H.; Yoshida, M.; Torii, S. unpublished results.