Novel Catalytic Functions of Hydrophobic Vitamin B12 in Electrochemical Carbon-Skeleton Rearrangements

Yukito Murakami, Yoshio Hisaeda

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The carbon-skeleton rearrangements as catalyzed by hydrophobic vitamin B12 derivatives were investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides with various electron-withdrawing groups were carried out, and the electrochemical carbon-skeleton rearrangements proceeded via formation of anionic intermediates. Substrates with two electron-withdrawing groups placed on the β-carbon atom with combination of one carboxylic ester and one of carboxylic ester, ace-tyl, and cyano moieties readily gave the corresponding rearrangement products which were derived from individual migration of the substituent groups. Substrates with only one of the electron-withdrawing groups, carboxylic ester, acetyl, and cyano, did not give any rearrangement product, but a substrate with one thioester group afforded the corresponding rearrangement product. The apparent migratory aptitude of electron-withdrawing groups was found to decrease in the order: COSR > COR > CO2R > CN. A hydrophobic vitamin B12 with the cyano moiety at the axial site of cobalt further enhanced the electrochemical carbon-skeleton rearrangement.

Original languageEnglish
Pages (from-to)1363-1368
Number of pages6
JournalPure and Applied Chemistry
Volume60
Issue number8
DOIs
Publication statusPublished - Jan 1 1988

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Vitamins
Vitamin B 12
Carbon
Esters
Electrons
Substrates
Cobalt
Electrolysis
Derivatives
Atoms

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Novel Catalytic Functions of Hydrophobic Vitamin B12 in Electrochemical Carbon-Skeleton Rearrangements. / Murakami, Yukito; Hisaeda, Yoshio.

In: Pure and Applied Chemistry, Vol. 60, No. 8, 01.01.1988, p. 1363-1368.

Research output: Contribution to journalArticle

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N2 - The carbon-skeleton rearrangements as catalyzed by hydrophobic vitamin B12 derivatives were investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides with various electron-withdrawing groups were carried out, and the electrochemical carbon-skeleton rearrangements proceeded via formation of anionic intermediates. Substrates with two electron-withdrawing groups placed on the β-carbon atom with combination of one carboxylic ester and one of carboxylic ester, ace-tyl, and cyano moieties readily gave the corresponding rearrangement products which were derived from individual migration of the substituent groups. Substrates with only one of the electron-withdrawing groups, carboxylic ester, acetyl, and cyano, did not give any rearrangement product, but a substrate with one thioester group afforded the corresponding rearrangement product. The apparent migratory aptitude of electron-withdrawing groups was found to decrease in the order: COSR > COR > CO2R > CN. A hydrophobic vitamin B12 with the cyano moiety at the axial site of cobalt further enhanced the electrochemical carbon-skeleton rearrangement.

AB - The carbon-skeleton rearrangements as catalyzed by hydrophobic vitamin B12 derivatives were investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides with various electron-withdrawing groups were carried out, and the electrochemical carbon-skeleton rearrangements proceeded via formation of anionic intermediates. Substrates with two electron-withdrawing groups placed on the β-carbon atom with combination of one carboxylic ester and one of carboxylic ester, ace-tyl, and cyano moieties readily gave the corresponding rearrangement products which were derived from individual migration of the substituent groups. Substrates with only one of the electron-withdrawing groups, carboxylic ester, acetyl, and cyano, did not give any rearrangement product, but a substrate with one thioester group afforded the corresponding rearrangement product. The apparent migratory aptitude of electron-withdrawing groups was found to decrease in the order: COSR > COR > CO2R > CN. A hydrophobic vitamin B12 with the cyano moiety at the axial site of cobalt further enhanced the electrochemical carbon-skeleton rearrangement.

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