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Substituent effects on the Bergman cyclization of ( Z )‐1,5‐hexadiyne‐3‐enes: a systematic computational study
Author(s) -
Prall Matthias,
Wittkopp Alexander,
Fokin Andrey A.,
Schreiner Peter R.
Publication year - 2001
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.1114
Subject(s) - exergonic reaction , chemistry , enediyne , substituent , density functional theory , enthalpy , basis set , medicinal chemistry , stereochemistry , computational chemistry , standard enthalpy of formation , catalysis , organic chemistry , thermodynamics , physics
The effects of several substituents (BH 2 , BF 2 , AlH 2 , CH 3 , C 6 H 5 , CN, COCH 3 , CF 3 , SiH 3 , NH 2 , NH 3 + , NO 2 , PH 2 , OH, OH 2 + , 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 (NH 3 + , NO 2 , OH, OH 2 + , 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 OH 2 + 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
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