@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",
note = "Funding Information: alkylatedc omplexw ith substrate4 seemst o be less Researchf rom the Ministry of Education, Science, was supported by a Grant-in-aid for Scientific favorabler elativet o that with others ubstrateds ue to Sports and Culture of Japan and a grant from the steric reasons.( iii) As for the product selectivity, Mazda Foundation. major products are ring-expandedo nes for all substratesW. hen evenn umbereds ubstrate(s2 and 4) are used, ester-migratedp roducts (C, and Cd) are obtainedt o somee xtent.S ince the 6-memberedri ng is structurally stable, the 5-membereds ubstrate( 1) readilyu nderwentr ing expansiont o affordB i. On the other hand, molar ratios of non-expandedp roducts (A + C) vs the ring-expansionp roduct(B) are much larger for reactionsw ith substrate2 than thosef or other reactionse xaminedh ere.",
year = "1997",
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",
}