The transfer of hydrogen from C-24 to C-25 in ergosterol biosynthesis

Abstract
A convenient synthesis of 3 hydroxytrisnorlanost-8-en-24-al and its conversion into [24-H3] lanosterol and [26,27-14C2] lanosterol is described. A method for the efficient incorporation of lanosterol into ergosterol by the whole cells of Saccharomyces cerevisiae is also described. It is shown that in the biosynthesis of ergosterol from doubly labelled lanosterol the C-24 hydrogen atom of lanosterol is trtained in ergosterol. On the basis of unambiguous degradations it is shown that the C-alkylation step in ergosterol biosynthesis is accompanied by the migration of a hydrogen atom from C-24 to C-25. The mechanism for the biosynthesis of the ergosterol side chain is presented. Mechanisms of other C-alkylation reactions are also discussed.