title: The energetic viability of an unexpected skeletal rearrangement in cyclooctatin biosynthesis.
abstract: Results of density functional theory calculations on possible mechanisms for formation of the diterpenoid cyclooctatin are described. These results are consistent with the involvement of an unexpected 1,3-alkyl shift that interconverts two cyclopropylcarbinyl carbocations and interchanges the positions of two carbon atoms in an 8-membered ring. Predictions for future experiments to provide further support of this mechanism also are described.
authors.affiliation: Department of Chemistry, Univeristy of California-Davis, Davis, CA 95616, USA. djtantillo@ucdavis.edu.
authors.forename: Young J
authors.initials: YJ
authors.lastname: Hong
authors.forename: Dean J
authors.initials: DJ
authors.lastname: Tantillo
mesh_terms: D004224:Diterpenes / Q000737:chemistry* / Q000378:metabolism*; D008245:Lysophospholipase / Q000378:metabolism; D015394:Molecular Structure; D011789:Quantum Theory; D013302:Streptomyces / Q000737:chemistry / Q000378:metabolism
chemical_list: D004224:Diterpenes; C078947:cyclooctatin; D008245:Lysophospholipase