1422529-17-6Relevant articles and documents
Nonstatistical dynamic effects in the thermal C2-C6 Diels-Alder cyclization of enyne-allenes
Samanta, Debabrata,Cinar, Mehmet Emin,Das, Kalpataru,Schmittel, Michael
, p. 1451 - 1462 (2013/03/28)
The Diels-Alder (DA) reaction channel of the thermal C2-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-C6/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.