Reduktive Co-Alkylierung von Heptamethyl-cobyrinat mit dem Methylthiomalonat (S)-Methyl-3-bromo-2-[(ethylthio) carbonyl]-2-methylpropanoat |
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Authors: | Susanna Müller Annemarie Wolleb Lorenz Walder Reinhart Keese |
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Abstract: | Reductive Co Alkylation of Heptamethyl Cobyrinate with the Methylthiomalonate (S)-Methyl 3-Bromo-2-(ethylthio)carbonyl]-2-methylpropanoate The 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 (pro-S)-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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