title: Transannular proton transfer in the cyclization of geranylgeranyl diphosphate to fusicoccadiene, a biosynthetic intermediate of fusicoccins.
abstract: Enzymatic cyclization of geranylgeranyl diphosphate to fusicoccadiene involves a transannular proton transfer process. Label distribution in the cyclized products derived from deuterium-labeled GGDPs showed that a proton generated from C-10 migrates to C-6 in the intermediary dolabellane framework prior to the second ring formation. Although a direct 1,5-proton transfer would achieve this process, semiempirical MO calculations suggested an alternative pathway, which involves successive 1,4- and 1,5-proton transfers using C-2 as a springboard.
authors.affiliation: Department of Bioresource Engineering, Yamagata University, Tsuruoka, Yamagata 997-8555, Japan.
authors.forename: Tomonobu
authors.initials: T
authors.lastname: Toyomasu
authors.forename: Mai
authors.initials: M
authors.lastname: Tsukahara
authors.forename: Hiromichi
authors.initials: H
authors.lastname: Kenmoku
authors.forename: Masahide
authors.initials: M
authors.lastname: Anada
authors.forename: Hajime
authors.initials: H
authors.lastname: Nitta
authors.forename: Junko
authors.initials: J
authors.lastname: Ohkanda
authors.forename: Wataru
authors.initials: W
authors.lastname: Mitsuhashi
authors.forename: Takeshi
authors.initials: T
authors.lastname: Sassa
authors.forename: Nobuo
authors.initials: N
authors.lastname: Kato
mesh_terms: D003500:Cyclization; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D011106:Polyisoprenyl Phosphates
chemical_list: D004224:Diterpenes; D011106:Polyisoprenyl Phosphates; C115566:dolabellane; C542617:fusicoccadiene; C002963:geranylgeranyl pyrophosphate