Transannular proton transfer in the cyclization of geranylgeranyl diphosphate to fusicoccadiene, a biosynthetic intermediate of fusicoccins.
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.
Toyomasu
Tomonobu
T
Department of Bioresource Engineering, Yamagata University, Tsuruoka, Yamagata 997-8555, Japan.
Tsukahara
Mai
M
Kenmoku
Hiromichi
H
Anada
Masahide
M
Nitta
Hajime
H
Ohkanda
Junko
J
Mitsuhashi
Wataru
W
Sassa
Takeshi
T
Kato
Nobuo
N
D003500:Cyclization; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D011106:Polyisoprenyl Phosphates
D004224:Diterpenes; D011106:Polyisoprenyl Phosphates; C115566:dolabellane; C542617:fusicoccadiene; C002963:geranylgeranyl pyrophosphate