Trichodiene biosynthesis and the stereochemistry of the enzymatic cyclization of farnesyl pyrophosphate |
| |
Authors: | David E Cane Hyun-Joon Ha Christopher Pargellis Felix Waldmeier Stephen Swanson Pushpalatha PN Murthy |
| |
Institution: | Department of Chemistry, Brown University, Providence, Rhode Island 02912 USA |
| |
Abstract: | Cyclization of trans,trans-1-3H2,12,13-14C]farnesyl pyrophosphate (2a) by a preparation of trichodiene synthetase isolated from the fungus, Trichothecium roseum, gave trichodiene (5a), which was shown by chemical degradation to retain both tritium atoms of the precursor at C-11. Incubation of 1S-1-3H,12,13-14C]farnesyl pyrophosphate (2b) and 1R-1-3H,12,13-14C]farnesyl pyrophosphate (2c) with trichodiene synthetase and degradation of the resulting labeled trichodienes, 5b and 5c, established that the displacement of the pyrophosphate moiety from C-1 of the precursor and formation of the new C-C bond in the formation of trichodiene takes place with net retention of configuration. These results are accounted for by an isomerization-cyclization mechanism involving the intermediacy of nerolidyl pyrophosphate (4). |
| |
Keywords: | To whom correspondence should be addressed |
本文献已被 ScienceDirect 等数据库收录! |
|