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Stereoselectivity and kinetics of [4 + 2] cycloaddition reaction of cyclopentadiene to para ‐substituted E‐2‐arylnitroethenes
Author(s) -
Jasiński Radomir,
Kwiatkowska Magdalena,
Barański Andrzej
Publication year - 2011
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1853
Subject(s) - chemistry , cyclopentadiene , cycloaddition , electrophile , stereoselectivity , substituent , aryl , reaction mechanism , computational chemistry , solvent effects , electrophilic substitution , medicinal chemistry , stereochemistry , solvent , organic chemistry , catalysis , alkyl
In spite of diversified electrophilicity of E‐2‐arylnitroethenes, their [4 + 2] cycloaddition reactions with cyclopentadiene leads to the corresponding 6‐ endo ‐aryl‐5‐ exo ‐nitronorbornenes and 6‐ exo ‐aryl‐5‐ endo ‐nitronorbornenes as the only reaction products. Stereoselectivity, substituent and solvent effects, and activation parameters, suggest that these reactions occur via a synchronous concerted mechanism on both competing pathways. The experimental results obtained are consistent with the data from B3LYP/6‐31G(d) calculations. Due to high electrophilicity of E‐2‐arylnitroethenes, the reactions studied should be considered as polar [4 + 2] cycloadditions. Copyright © 2011 John Wiley & Sons, Ltd.