Substituent effects on the Bergman cyclization of (Z)-1,5-hexadiyne-3-enes: a systematic computational study

Autor:	Peter R. Schreiner, Andrey A. Fokin, Matthias Prall, Alexander Wittkopp
Rok vydání:	2001
Předmět:	Exergonic reaction 010405 organic chemistry Stereochemistry Enthalpy Substituent General Chemistry 010402 general chemistry 01 natural sciences 0104 chemical sciences Computational Mathematics chemistry.chemical_compound chemistry Bergman cyclization Enediyne Basis set
Zdroj:	Journal of Computational Chemistry. 22:1605-1614
ISSN:	1096-987X 0192-8651
Popis:	The effects of several substituents (BH2, BF2, AlH2, CH3, C6H5, CN, COCH3, CF3, SiH3, NH2, NH3+, NO2, PH2, OH, OH2+, SH, F, Cl, Br) on the Bergman cyclization of (Z)-1,5-hexadiyne-3-ene (enediyne, 3) were investigated at the Becke–Lee–Yang–Parr (BLYP) density functional (DFT) level employing a 6-31G* basis set. Some of the substituents (NH3+, NO2, OH, OH2+, F, Cl, Br) are able to lower the barrier (up to a minimum of 16.9 kcal mol−1 for difluoro-enediyne 7rr) and the reaction enthalpy (the cyclization is predicted to be exergonic for OH2+ and F) compared to the parent system giving rise to substituted 1,4-dehydrobenzenes at physiological temperatures. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1605–1614, 2001
Databáze:	OpenAIRE
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