Computational studies on biosynthetic carbocation rearrangements leading to sativene, cyclosativene, alpha-ylangene, and beta-ylangene.
In this paper, we describe theoretical studies, using gas-phase quantum chemical calculations, on carbocationic rearrangement pathways leading to the sesquiterpenes sativene, cyclosativene, alpha-ylangene, and beta-ylangene. For all four sesquiterpene natural products, viable pathways are presented, and these are compared both to mechanistic proposals found in the literature, and in certain cases to alternative stereochemical and rearrangement possibilities, thus providing a basis for comparison to experimental results. We find that these four sesquiterpenes likely arise from a common bicyclic intermediate and, furthermore, that the computed pathways are mostly in agreement with previous mechanistic proposals, although the few differences that we have uncovered are significant. Additionally, the potential energy profiles of the pathways are found to be very flat, supporting the notion that following the initial ionization of farnesyl diphosphate, minimal enzymatic intervention may be required for the generation of such sesquiterpenes.
Lodewyk
Michael W
MW
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, USA.
Gutta
Pradeep
P
Tantillo
Dean J
DJ
D000465:Algorithms; D001688:Biological Products / Q000096:biosynthesis / Q000138:chemical synthesis; D002244:Carbon / Q000737:chemistry / Q000378:metabolism; D002412:Cations; D003500:Cyclization; D008962:Models, Theoretical; D011106:Polyisoprenyl Phosphates / Q000737:chemistry / Q000378:metabolism; D011789:Quantum Theory; D012717:Sesquiterpenes / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism; D013237:Stereoisomerism; D013816:Thermodynamics
D001688:Biological Products; D002412:Cations; D011106:Polyisoprenyl Phosphates; D012717:Sesquiterpenes; C430146:sativene; D002244:Carbon; C004808:farnesyl pyrophosphate