Reduktive Co‐Alkylierung von Heptamethyl‐cobyrinat mit dem Methylthiomalonat (S)‐Methyl‐3‐bromo‐2‐[(ethylthio) carbonyl]‐2‐methylpropanoat

Abstract
Reductive Co Alkylation of Heptamethyl Cobyrinate with the Methylthiomalonate (S)‐Methyl 3‐Bromo‐2‐[(ethylthio)carbonyl]‐2‐methylpropanoateThe methylthiomalonate(−)‐(S)‐Methyl 3‐bromo‐2‐[(ethylthio)carbonyl]‐2‐methylpropanoate(5a)was prepared from dimethyl methylmalonate in five steps via the stereospecific cleavage of the (proS)‐ester group of 1 with pig‐liver esterase in an overall yield of 26.5% (Scheme 4a). Reductive Co alkylation of heptamethyl Coβ‐perchlorato cob (II)yrinate (8) with 5a by electrosynthesis lead to the alkylcobalt complex 9a in 40% yield (Scheme 4b). The O2‐dependent reactions of the methyhnalonyl fragment produced by photolysis of 9a and its deuterated derivative 9c are reported (Scheme 5).

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