Hydrophobic vitamin B12. X.F steric effect in electrochemical carbon-skeleton rearrangement catalyzed by hydrophobic vitamin B12in nonaqueous media

Yukito Murakami, Yoshio Hisaeda, Toshiaki Ozaki

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

A steric effect in the carbon-skeleton rearrangement catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester]ClO4, 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, I-bromo-2-tert-butoxycarbonyl-2-ethoxycarbonylpropane 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]ClO4 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 to the rate-determining step.

Original languageEnglish
Pages (from-to)77-89
Number of pages13
JournalJournal of Coordination Chemistry
Volume23
Issue number1-4
DOIs
Publication statusPublished - Jun 1 1991

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vitamins
Vitamins
Vitamin B 12
musculoskeletal system
esters
Esters
Carbon
carbon
acetic acid
Acetic acid
Acetic Acid
aptitude
Dimethylformamide
Atoms
electrolysis
perchlorates
Electrolysis
halides
atoms
products

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Hydrophobic vitamin B12. X.F steric effect in electrochemical carbon-skeleton rearrangement catalyzed by hydrophobic vitamin B12in nonaqueous media. / Murakami, Yukito; Hisaeda, Yoshio; Ozaki, Toshiaki.

In: Journal of Coordination Chemistry, Vol. 23, No. 1-4, 01.06.1991, p. 77-89.

Research output: Contribution to journalArticle

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AB - A steric effect in the carbon-skeleton rearrangement catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester]ClO4, 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, I-bromo-2-tert-butoxycarbonyl-2-ethoxycarbonylpropane 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]ClO4 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 to the rate-determining step.

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