The interaction between a vitamin B,, derivative containing a peripheral C,, alkyl chain (see la) and a (methy1)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/H,O, and when both the substrate and the catalyst had an octadecyl substituent capable of hydrophobic interactions.Introduction. -Adenosylcobalamin acts as coenzyme for a series of biological rearrangements where a group X and a H-atom exchange places on adjacent C-atoms (Scheme l a ) . There are twelve known reactions following this general scheme where the group X is a hydroxy, an amino or, in the C-skeleton rearrangements, a thioester, an acrylate, or a glycinate moiety. From all these reactions, only the one involving the methylmalonyl-succinyl transformation (Scheme 1,b) occurs in higher organisms and mammals, all the other examples being part of bacteria metabolism. In the particular case of a thioester group, the methylmalonyl-CoA mutase catalyzes the 1,2-migration with retention of configuration [ 11.
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