The Co(i) induced methylmalonyl-succinyl rearrangement in a model for the coenzyme B12 dependent methylmalonyl-CoA mutase

Abstract

The rearrangement of 2-bromomethyl-2-methylmonothiomalonates to succinyl derivatives was found to take place in quantitative yields in the presence of one molar equivalent of Co(I) generated by the reduction of heptamethyl Co(II)yrinate perchlorate with NaBH4 or electrochemically. The chiral thiomalonate gave racemic succinate.

Chemistry and Enzymology of Vitamin B12

“…Sun and Darbre reported a very intriguing set of experiments aimed at modeling the methylmalonylCoA mutase rearrangement. The synthesis of alkylcobalt corrinoids is normally carried out by treating reduced cobalt corrinoids with a large molar excess of alkylating agent (frequently halides).…”

Synthesis, characterization and catalytic function of a B12-hyperbranched polymer

“…Due to their rich redox and coordination chemistry, vitamin B 12 and derivatives are used as efficient homogenous catalysts in a number of chemical transformations 5, 6 such as electron transfer reactions 7 and radical involved organic reactions. 8- 10 We have been dealing with a hydrophobic vitamin B 12 , heptamethyl cobyrinate perchlorate, [Cob(II)7C 1 ester], which has ester groups in place of the peripheral amide moieties of vitamin B 12 and succeeded in performing various electroorganic reactions (Chart 1). 11- 14 In order to develop a good catalytic system, several methods for immobilization of vitamin B 12 derivatives on a solid-phase support have been reported.…”

Learning from B12 enzymes: biomimetic and bioinspired catalysts for eco-friendly organic synthesis

“…Construction of sustainable catalytic systems inspired by B 12 enzymes is another important issue that must be addressed for green chemistry. Due to the above-mentioned unique redox and coordination chemistry, vitamin B 12 and its derivatives [ 22 ] are used as effective homogenous catalysts in various organic reactions [ 23 – 25 ], although an excess of chemical reductants are often used to activate B 12 to the Co(I) species. Green catalytic systems capable of activating B 12 have not been reported in the literature, with the exception of electrocatalytic systems [ 26 – 27 ].…”