Hydrophobic Vitamin B12. X. Steric Effect in Electrochemical Carbon-Skeleton Rearrangement Catalyzed by Hydrophobic Vitamin B12 in Nonaqueous Media

Autor:	Yukito Murakami, Toshiaki Ozaki, Yoshio Hisaeda
Rok vydání:	1991
Předmět:	Steric effects chemistry.chemical_classification Reaction mechanism Electrochemistry Medicinal chemistry Catalysis Acetic acid chemistry.chemical_compound Perchlorate chemistry Materials Chemistry Organic chemistry Rearrangement reaction Physical and Theoretical Chemistry Alkyl
Zdroj:	Journal of Coordination Chemistry. 23:77-89
ISSN:	1029-0389 0095-8972
DOI:	10.1080/00958979109408244
Popis:	A steric effect in the carbon-skeleton rearrangement catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester]C104, was investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides having two carboxylic ester groups of different bulkiness on the same carbon atom, such as 2,2-bis(ethoxycarbonyl)-l-bromopropane, l-bromo-2-tert-butoxycarbonyl-2-ethoxy-carbonylpropane, l-bromo-2-cyclohexyloxycarbonyl-2-ethoxycarbonylpropane, and l-bromo-2-ethoxy-carbonyl-2-phenoxycarbonylpropane, were carried out in N,N-dimethylformamide, as catalyzed by [Cob(II)7C1ester]CIO4, to give the corresponding ester-migrated products in the dark at—1.5 V vs SCE in the presence of acetic acid and at—2.0 V vs SCE without acetic acid. As regards a correlation between bulkiness of an ester group and a migration aptitude, a smaller ester group tends to migrate to the adjacent carbon atom more readily than a larger one. The origin of such a steric effect is discussed with attention...
Databáze:	OpenAIRE
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