Vitamin B12 model complex catalyzed methyl transfer reaction to alkylthiol under electrochemical conditions with sacrificial electrode

Ling Pan, Hisashi Shimakoshi, Takahiro Masuko, Yoshio Hisaeda

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8 Citations (Scopus)

Abstract

Catalytic methyl transfer reactions from methyl tosylate to 1-octanethiol catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester] ClO4, were investigated under electrochemical conditions. As a model study for the cobalamin-dependent methyl transfer reaction from methyltetrahydrofolate to homocysteine, controlled-potential electrolyses were carried out at -1.0 V vs. Ag/AgCl using a zinc plate as the sacrificial anode at 50 °C in the dark. A turnover behaviour for the methyl transfer reaction was observed for the first time under non-enzymatic reaction conditions. Co(I) species, which is generated from the continuous electrolysis of [Cob(II)7C 1ester]ClO4, and its methylated CH3-Co complex were found to be important intermediates. The mechanism for such a methyl transfer reaction was investigated by product analysis, electronic spectroscopy and ESR spin-trapping experiments. A simple vitamin B12 model complex was also utilized as the catalyst for the methyl transfer reaction.

Original languageEnglish
Pages (from-to)9898-9905
Number of pages8
JournalDalton Transactions
Issue number44
DOIs
Publication statusPublished - Nov 16 2009

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Vitamin B 12
Electrolysis
Electrodes
Homocysteine
Paramagnetic resonance
Byproducts
Zinc
Anodes
Spectroscopy
Catalysts
perchlorate
Experiments

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

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title = "Vitamin B12 model complex catalyzed methyl transfer reaction to alkylthiol under electrochemical conditions with sacrificial electrode",
abstract = "Catalytic methyl transfer reactions from methyl tosylate to 1-octanethiol catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester] ClO4, were investigated under electrochemical conditions. As a model study for the cobalamin-dependent methyl transfer reaction from methyltetrahydrofolate to homocysteine, controlled-potential electrolyses were carried out at -1.0 V vs. Ag/AgCl using a zinc plate as the sacrificial anode at 50 °C in the dark. A turnover behaviour for the methyl transfer reaction was observed for the first time under non-enzymatic reaction conditions. Co(I) species, which is generated from the continuous electrolysis of [Cob(II)7C 1ester]ClO4, and its methylated CH3-Co complex were found to be important intermediates. The mechanism for such a methyl transfer reaction was investigated by product analysis, electronic spectroscopy and ESR spin-trapping experiments. A simple vitamin B12 model complex was also utilized as the catalyst for the methyl transfer reaction.",
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T1 - Vitamin B12 model complex catalyzed methyl transfer reaction to alkylthiol under electrochemical conditions with sacrificial electrode

AU - Pan, Ling

AU - Shimakoshi, Hisashi

AU - Masuko, Takahiro

AU - Hisaeda, Yoshio

PY - 2009/11/16

Y1 - 2009/11/16

N2 - Catalytic methyl transfer reactions from methyl tosylate to 1-octanethiol catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester] ClO4, were investigated under electrochemical conditions. As a model study for the cobalamin-dependent methyl transfer reaction from methyltetrahydrofolate to homocysteine, controlled-potential electrolyses were carried out at -1.0 V vs. Ag/AgCl using a zinc plate as the sacrificial anode at 50 °C in the dark. A turnover behaviour for the methyl transfer reaction was observed for the first time under non-enzymatic reaction conditions. Co(I) species, which is generated from the continuous electrolysis of [Cob(II)7C 1ester]ClO4, and its methylated CH3-Co complex were found to be important intermediates. The mechanism for such a methyl transfer reaction was investigated by product analysis, electronic spectroscopy and ESR spin-trapping experiments. A simple vitamin B12 model complex was also utilized as the catalyst for the methyl transfer reaction.

AB - Catalytic methyl transfer reactions from methyl tosylate to 1-octanethiol catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester] ClO4, were investigated under electrochemical conditions. As a model study for the cobalamin-dependent methyl transfer reaction from methyltetrahydrofolate to homocysteine, controlled-potential electrolyses were carried out at -1.0 V vs. Ag/AgCl using a zinc plate as the sacrificial anode at 50 °C in the dark. A turnover behaviour for the methyl transfer reaction was observed for the first time under non-enzymatic reaction conditions. Co(I) species, which is generated from the continuous electrolysis of [Cob(II)7C 1ester]ClO4, and its methylated CH3-Co complex were found to be important intermediates. The mechanism for such a methyl transfer reaction was investigated by product analysis, electronic spectroscopy and ESR spin-trapping experiments. A simple vitamin B12 model complex was also utilized as the catalyst for the methyl transfer reaction.

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