175. Model studies for the coenzyme-B12-catalyzed methylmalonyl→succinyl rearrangement. The importance of hydrophobic peripheral associations

Article abstract of DOI:10.1002/hlca.19960790807

The interaction between a vitamin B₁₂ derivative containing a peripheral C₁₈ alkyl chain (see 1a) and a (methyl)thiomalonate substrate bearing 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 (see Scheme 3). Increased yields of the succinate relative to the reduction product were obtained (2:3 ratio), when the reaction was run in MeOH/H₂O, and when both the substrate and the catalyst had an octadecyl substituent capable of hydrophobic interactions.