W. Boland et al., BIOSYNTHESIS OF C-11 AND C-16 HOMOTERPENES IN HIGHER-PLANTS - STEREOCHEMISTRY OF THE C-C-BOND CLEAVAGE REACTION, Tetrahedron, 54(49), 1998, pp. 14725-14736
In higher plants the C-11 homoterpene 4,8-dimethylnona-1,3,7-triene (1
) originates from oxidative degradation of nerolidol (3) or geranylace
tone (4). The geometry of the transition state of bond cleavage has be
en shown to be syn-periplanar, for both 3 and 4 by application of chir
ally 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. (C)
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