Biosynthesis of C11 and C16 homoterpenes in higher plants; stereo- chemistry of the C-C-bond cleavage reaction

Article abstract of DOI:10.1016/S0040-4020(98)00902-8

In higher plants the C₁₁ homoterpene 4,8-dimethylnona-1,3,7-triene (1) originates from oxidative degradation of nerolidol (3) or geranylacetone (4). The geometry of the transition state of bond cleavage has been shown to be syn-periplanar, for both 3 and 4 by application of chirally labelled, deuterated precursors to flowers of Magnolia liliiflora nigra or leaves of the Lima bean Phaseolus lunatus. The synthesis of the deuterated, chiral metabolic probes 3 and 8 from nor-farnesene (5), via the enantiomeric epoxides (2S,3R)-6 and ent-6, is described.