Photochemical generation and reversible cycloaromatization of a nine-membered ring cyclic enediyne.
Irradiation of the nine-membered ring enediyne precursor, which has one of its triple bonds masked as cyclopropenone, efficiently (Phi = 0.34) generates the reactive 4,5-benzocyclonona-2,6-diynol. The latter rapidly equilibrates with the corresponding 1,4-didehydronaphthalene diradical and then undergoes rate-limiting hydrogen abstraction to produce the ultimate product of the Bergman cyclization, benz[f]indanol.
Pandithavidana
Dinesh R
DR
Department of Chemistry, University of Georgia, Athens, Georgia 30677, USA.
Poloukhtine
Andrei
A
Popik
Vladimir V
VV
D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D003500:Cyclization; D003521:Cyclopropanes / Q000138:chemical synthesis / Q000737:chemistry*; D004278:DNA, Superhelical / Q000737:chemistry; D003851:Deoxyribonucleases / Q000737:chemistry; D007189:Indans / Q000138:chemical synthesis* / Q000737:chemistry*; D007700:Kinetics; D009281:Naphthalenes / Q000138:chemical synthesis / Q000737:chemistry*; D055668:Photochemical Processes; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics
D000480:Alkynes; D003521:Cyclopropanes; D004278:DNA, Superhelical; D007189:Indans; D009281:Naphthalenes; C120343:cyclopropenone; D003851:Deoxyribonucleases