Two-photon photochemical generation of reactive enediyne.
p-Quinoid cyclopropenone-containing enediyne precursor (1) has been synthesized by monocyclopropanation of one of the triple bonds in p-dimethoxy-substituted 3,4-benzocyclodeca-1,5-diyne followed by oxidative demethylation. Cyclopropenone 1 is stable up to 90 degrees C but readily produces reactive enediyne 2 upon single-photon (Phi(300)(nm) = 0.46) or two-photon (sigma(800 nm) = 0.5 GM) photolysis. The photoproduct 2 undergoes Bergman cyclization at 40 degrees C with the lifetime of 88 h.
Poloukhtine
Andrei
A
Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403, USA.
Popik
Vladimir V
VV
D003500:Cyclization; D003521:Cyclopropanes / Q000138:chemical synthesis* / Q000737:chemistry; D053281:Enediynes / Q000138:chemical synthesis* / Q000737:chemistry; D010777:Photochemistry; D017785:Photons
D003521:Cyclopropanes; D053281:Enediynes; C120343:cyclopropenone