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Updated: May 14, 2026

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
Nonstatistical dynamic effects in the thermal C2-C6 Diels-Alder cyclization of enyne-allenes
Debabrata Samanta1, Mehmet Emin Cinar, Kalpataru Das
1Department of Chemistry and Biology, Universität Siegen, Adolf-Reichwein-Strasse, D-57068 Siegen, Germany.
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.
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