Hydrophobic vitamin B12. V Electrochemical carbon-skeleton rearrangement as catalyzed by hydrophobic vitamin B12 : Reaction mechanisms and migratory aptitude of functional groups.
Hydrophobic vitamin B12. V Electrochemical carbon-skeleton rearrangement as catalyzed by hydrophobic vitamin B12 : Reaction mechanisms and migratory aptitude of functional groups.
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疏水性维生素B12。
DOI：
10.1246/bcsj.60.311
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发表时间：
1987
影响因子：
4
通讯作者：
Y. Matsuda
中科院分区：
文献类型：
--
作者：
Y. Murakami;Y. Hisaeda;T. Ozaki;Takako Tashiro;T. Ohno;Yutaro Tani;Y. Matsuda
在电化学条件下研究了钴啉七甲酯高氯酸盐[Cob（II）7 C1 ester] ClO 4催化的碳骨架重排。2，2-双的控制电位电解在N，N-二甲基甲酰胺中，[Cob（II）7 C1 ester] ClO_4催化甲基丙二酰辅酶A重排的模型底物--（乙氧羰基）-1-溴丙烷重排，得到1，2-双（乙氧羰基）丙烷，作为一个主要的一个在-1.5V vs. SCE在乙酸的存在下，在电位比-1.8V vs. SCE在黑暗中没有乙酸。电化学碳骨架重排被假定为通过形成阴离子中间体进行。1-溴-2-氰基-2-乙氧羰基丙烷、2-乙酰基-1-溴-2-乙氧羰基丙烷和1-溴-2-乙硫基羰基丙烷与[Cob（II）7 Cl酯] ClO_4的电解反应也得到相应的碳骨架重排产物。结果表明，具有两个吸电子基团的基底具有较好的电性能。
The carbon-skeleton rearrangements as catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester]ClO4, were investigated under electrochemical conditions. The controlled-potential electrolysis of 2,2-bis(ethoxycarbonyl)-1-bromopropane, which is considered to be a model substrate for methylmalonyl–CoA mutase, was catalyzed by [Cob(II)7C1ester]ClO4 in N,N-dimethylformamide to give the rearrangement product, 1,2-bis(ethoxycarbonyl)propane, as a major one at −1.5V vs. SCE in the presence of acetic acid and at potentials more cathodic than −1.8V vs. SCE without acetic acid in the dark. The electrochemical carbon-skeleton rearrangement was postulated to proceed via formation of anionic intermediates. The electrolyses of 1-bromo-2-cyano-2-ethoxycarbonylpropane, 2-acetyl-1-bromo-2-ethoxycarbonylpropane, and 1-bromo-2-[(ethylthio)carbonyl]propane with [Cob(II)7C1ester]ClO4 also afforded the corresponding carbon-skeleton rearrangement products. The results indicated that substrates with two electron-withdraw...