Use of deuterium as a tracer with 13C nuclear magnetic resonance spectroscopy in following deuteride migration in terpenoid biosynthesis: mechanism of geranylgeranyl pyrophosphate cyclisation in fusicoccin biosynthesis

Abstract

Three of the four (4R) mevalonoid atoms retained in fusicoccin (1a) have been located at C-7, C-15, and C-23 by ¹³C n.m.r. spectroscopy, following the incorporation of [3-¹³C, 4-²H₂]mevalonolactone; a 1,2-deuteride shift is demonstrated in the formation of the bicyclic intermediate (3), whilst two consecutive 1,2-deuteride shifts are established during the further cyclisation of (3) to (1a).