Enhancement of the reactivity of photochemically generated enediynes via keto-enol tautomerization.
Ten- and eleven-membered-ring cyclic enediynes that possess a carbonyl group in a beta position with respect to the one of acetylenic termini undergo very facile cycloaromatization at ambient temperatures. Kinetic data and deuterium-labeling experiments indicate that this reaction proceeds via rate-determining tautomerization to the allene-eneyne form followed by very rapid Myers-Saito cyclization.
Karpov
Grigori
G
Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA.
Kuzmin
Alexander
A
Popik
Vladimir V
VV
D000438:Alcohols / Q000737:chemistry*; D053281:Enediynes / Q000737:chemistry*; D006844:Hydrocarbons, Cyclic / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D007700:Kinetics; D010777:Photochemistry; D013056:Spectrophotometry, Ultraviolet
D000438:Alcohols; D053281:Enediynes; D006844:Hydrocarbons, Cyclic; D007659:Ketones