T. Darbre et al., MODEL STUDIES FOR THE COENZYME-B-12-CATALYZED METHYLMALONYL-]SUCCINYLREARRANGEMENT - THE IMPORTANCE OF HYDROPHOBIC PERIPHERAL ASSOCIATIONS, Helvetica Chimica Acta, 79(8), 1996, pp. 2100-2113
The interaction between a vitamin B-12 derivative containing a periphe
ral C-18 alkyl chain (see 1a) and a (methyl)thiomalonate substrate bea
ring alkyl chains of various length at the thioester group (see 5) was
investigated. A catalytic cycle was established for the methylmalonyl
-->succinyl rearrangement by using electrochemistry and photolysis (se
e Scheme 3). Increased yields of the succinate relative to the reducti
on product were obtained (2:3 ratio), when the reaction was run in MeO
H/H2O, and when both the substrate and the catalyst had an octadecyl s
ubstituent capable of hydrophobic interactions.