Nonstatistical dynamic effects in the thermal C2-C6 Diels-Alder cyclization of enyne-allenes
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.
Samanta, Debabrata,Cinar, Mehmet Emin,Das, Kalpataru,Schmittel, Michael
p. 1451 - 1462
(2013/03/28)
Intramolecular dehydro Diels-Alder reactions of diarylacetylenes: Switching between benzo[b]- and benzo[c]fluorenones as products by controlling the rearrangement of cyclic allene intermediates
Thermal cyclization of 1-[2-(arylethynyl)phenyl] -3-trimethylsilylpropynones affords a mixture of benzo[b]fluorenones and benzo[c]fluorenones. The ratio of the two isomers can be efficiently varied between 100:0 and 0:100 by introducing substituents with
Rodri?guez, David,Marti?nez-Espero?n, Mari?a Fernanda,Navarro-Va?zquez, Armando,Castedo, Luis,Domi?nguez, Domingo,Saa?, Carlos
p. 3842 - 3848
(2007/10/03)
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