4β-(tert-butyl)-lα-(l-methylvinyl)cyclohexanecarboxylic acid 77 and its derivatives amide 75, methyl ester 79, and phenyl thioester 80 were synthesed. They were treated with catalytic amount of hydridocobalamin in the presence of activated zinc dust in acetic acid. Rearranged products of about 3% were detected for the reaction of phenyl thioester 80. No rearrangement reactions, but only direct reductions, were observed for amide 75, acid 77 and methyl ester 79....[ Read more ]

4β-(tert-butyl)-lα-(l-methylvinyl)cyclohexanecarboxylic acid 77 and its derivatives amide 75, methyl ester 79, and phenyl thioester 80 were synthesed. They were treated with catalytic amount of hydridocobalamin in the presence of activated zinc dust in acetic acid. Rearranged products of about 3% were detected for the reaction of phenyl thioester 80. No rearrangement reactions, but only direct reductions, were observed for amide 75, acid 77 and methyl ester 79.

A series of 2-(4-tert-butyl-l-cyclohexenyl)-2-methylpropionic acid derivatives ethyl ester 82, methyl ester 84 and phenyl thioester 85 were also synthesed. Similarly, they were treated with catalytic amount of hydridocobalamin in the presence of activated zinc dust in glacial acetic acid. Slow saturation reactions were observed for these compounds. In the reaction of the phenyl thioester 85, 0.7% of rearranged product was detected. But, no rearrangement reactions were observed for ethyl ester 82 and methyl ester 84.

The detection of the rearranged products in the reactions of phenyl thioesters 80 and 85 indicate that the six alkylcobalamins and alkoxylcobalamins may be the intermediates of the rearrangement reactions.