856219-71-1Relevant articles and documents
Kinetic isotope effects in the thermal C2-C6 cyclization of enyne-allenes: Experimental evidence supports a stepwise mechanism
Schmittel, Michael,Vavilala, Chandrasekhar
, p. 4865 - 4868 (2005)
Kinetic isotope effects suggest that the thermal C2-C 6 cyclization of enyne-allenes proceeds through a stepwise diradical mechanism. This is even true if steric bulk at the alkyne terminus is large, contrary to theoretical predictio
Photochemical C2-C6 cyclization of enyne-allenes: Detection of a fulvene triplet diradical in the laser flash photolysis
Bucher, Goetz,Mahajan, Atul A.,Schmittel, Michael
supporting information; scheme or table, p. 8815 - 8828 (2009/04/11)
(Chemical Equation Presented) A series of enyne-allenes, with and without benzannulation at the ene moiety and equipped with aromatic and carbonyl groups as internal triplet sensitizer units at the allene terminus, was synthesized. Both sets, the cyclohexenyne-allenes and benzenyne-allenes, underwent thermal C2-C6 cyclization exclusively to formal ene products. In contrast, the photochemical C2-C6 cyclization of enyne-allenes provided formal Diels-Alder and/or ene products, with higher yields for the benzannulated systems. A raise of the temperature in the photochemical cyclization of enyne-allene 1b′ led to increasing amounts of the ene product in relation to that of the formal Diels-Alder product. Laser flash photolysis at 266 and 355 nm as well as triplet quenching studies for 1b,b′ indicated that the C2-C6 cyclization proceeds via the triplet manifold. On the basis of a density functional theory (DFT) study, a short-lived transient (r = 30 ns) was assigned as a triplet allene, while a long-lived transient (τ = 33 μs) insensitive to oxygen was assigned as fulvene triplet diradical. An elucidation of the reaction mechanism using extensive DFT computations allowed rationalization of the experimental product ratio and its temperature dependence.
