Hydrophobic vitamin B12. Part 14. Ring-expansion reactions catalyzed by hydrophobic vitamin B12 under electrochemical conditions in nonaqueous medium

Yoshio Hisaeda, Junji Takenaka, Yukito Murakami

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The electrolysis of alicyclic ketones (5, 6, 7, and 8-membered rings) with a carboxylic ester and a bromomethyl group was carried out in N,N-dimethylformamide in the presence of a catalytic amount of heptamethyl cobyrinate perchlorate under various reaction conditions. The ring-expansion reaction largely proceeded at -2.0 V vs sce for all the substrates. The electrolysis plausibly proceeds as follows: the Co(II) complex as a catalyst is electrochemically reduced to the Co(I) species; the corresponding alkylated complex is generated by reaction of the supernucleophilic Co(I) species with an alicyclic bromide; the alkylated complex is subsequently decomposed by electrolysis to afford the final products; and the cobalt complex acts as a mediator repeatedly.

Original languageEnglish
Pages (from-to)2165-2172
Number of pages8
JournalElectrochimica Acta
Volume42
Issue number13-14
DOIs
Publication statusPublished - Jan 1 1997

Fingerprint

Vitamins
Vitamin B 12
Electrolysis
Dimethylformamide
Cobalt
Ketones
Bromides
Esters
Catalysts
Substrates

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Electrochemistry

Cite this

Hydrophobic vitamin B12. Part 14. Ring-expansion reactions catalyzed by hydrophobic vitamin B12 under electrochemical conditions in nonaqueous medium. / Hisaeda, Yoshio; Takenaka, Junji; Murakami, Yukito.

In: Electrochimica Acta, Vol. 42, No. 13-14, 01.01.1997, p. 2165-2172.

Research output: Contribution to journalArticle

@article{0977ac93293f49da88b6e6a840f23ab6,
title = "Hydrophobic vitamin B12. Part 14. Ring-expansion reactions catalyzed by hydrophobic vitamin B12 under electrochemical conditions in nonaqueous medium",
abstract = "The electrolysis of alicyclic ketones (5, 6, 7, and 8-membered rings) with a carboxylic ester and a bromomethyl group was carried out in N,N-dimethylformamide in the presence of a catalytic amount of heptamethyl cobyrinate perchlorate under various reaction conditions. The ring-expansion reaction largely proceeded at -2.0 V vs sce for all the substrates. The electrolysis plausibly proceeds as follows: the Co(II) complex as a catalyst is electrochemically reduced to the Co(I) species; the corresponding alkylated complex is generated by reaction of the supernucleophilic Co(I) species with an alicyclic bromide; the alkylated complex is subsequently decomposed by electrolysis to afford the final products; and the cobalt complex acts as a mediator repeatedly.",
author = "Yoshio Hisaeda and Junji Takenaka and Yukito Murakami",
year = "1997",
month = "1",
day = "1",
doi = "10.1016/S0013-4686(97)85494-1",
language = "English",
volume = "42",
pages = "2165--2172",
journal = "Electrochimica Acta",
issn = "0013-4686",
publisher = "Elsevier Limited",
number = "13-14",

}

TY - JOUR

T1 - Hydrophobic vitamin B12. Part 14. Ring-expansion reactions catalyzed by hydrophobic vitamin B12 under electrochemical conditions in nonaqueous medium

AU - Hisaeda, Yoshio

AU - Takenaka, Junji

AU - Murakami, Yukito

PY - 1997/1/1

Y1 - 1997/1/1

N2 - The electrolysis of alicyclic ketones (5, 6, 7, and 8-membered rings) with a carboxylic ester and a bromomethyl group was carried out in N,N-dimethylformamide in the presence of a catalytic amount of heptamethyl cobyrinate perchlorate under various reaction conditions. The ring-expansion reaction largely proceeded at -2.0 V vs sce for all the substrates. The electrolysis plausibly proceeds as follows: the Co(II) complex as a catalyst is electrochemically reduced to the Co(I) species; the corresponding alkylated complex is generated by reaction of the supernucleophilic Co(I) species with an alicyclic bromide; the alkylated complex is subsequently decomposed by electrolysis to afford the final products; and the cobalt complex acts as a mediator repeatedly.

AB - The electrolysis of alicyclic ketones (5, 6, 7, and 8-membered rings) with a carboxylic ester and a bromomethyl group was carried out in N,N-dimethylformamide in the presence of a catalytic amount of heptamethyl cobyrinate perchlorate under various reaction conditions. The ring-expansion reaction largely proceeded at -2.0 V vs sce for all the substrates. The electrolysis plausibly proceeds as follows: the Co(II) complex as a catalyst is electrochemically reduced to the Co(I) species; the corresponding alkylated complex is generated by reaction of the supernucleophilic Co(I) species with an alicyclic bromide; the alkylated complex is subsequently decomposed by electrolysis to afford the final products; and the cobalt complex acts as a mediator repeatedly.

UR - http://www.scopus.com/inward/record.url?scp=0030697622&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0030697622&partnerID=8YFLogxK

U2 - 10.1016/S0013-4686(97)85494-1

DO - 10.1016/S0013-4686(97)85494-1

M3 - Article

VL - 42

SP - 2165

EP - 2172

JO - Electrochimica Acta

JF - Electrochimica Acta

SN - 0013-4686

IS - 13-14

ER -