title: Nonstatistical dynamic effects in the thermal C2-C6 Diels-Alder cyclization of enyne-allenes.
abstract: The Diels-Alder (DA) reaction channel of the thermal C(2)-C(6) (Schmittel) cyclization of enyne-allenes is studied computationally and experimentally evaluating the influence of temperature on product ratios. Remote substituents at the alkyne terminus influence the mechanism of the C(2)-C(6)/DA cyclization steering it either to a stepwise or a concerted course. Temperature independent product ratios, selectivity of product formation, and computational results obtained at (U)BLYP/6-31G(d) level unveil a mechanism that is strongly controlled by nonstatistical dynamics.
authors: Department of Chemistry and Biology, Universität Siegen, Adolf-Reichwein-Strasse, D-57068 Siegen, Germany.
authors: Debabrata
authors: D
authors: Samanta
authors: Mehmet Emin
authors: ME
authors: Cinar
authors: Kalpataru
authors: K
authors: Das
authors: Michael
authors: M
authors: Schmittel