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Density functional study of the relative reactivity in the concerted 1,3‐dipolar cycloaddition of nitrile ylide to disubstituted ethylenes
Author(s) -
Liao HsinYi,
Su MingDer,
Chung WenSheng,
Chu SanYan
Publication year - 2001
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.1062
Subject(s) - cycloaddition , chemistry , nitrile , reactivity (psychology) , polar effect , 1,3 dipolar cycloaddition , density functional theory , ylide , dipole , computational chemistry , photochemistry , medicinal chemistry , catalysis , organic chemistry , medicine , alternative medicine , pathology
Density functional theory was used to perform a theoretical evaluation of ( E )‐1,2‐disubstituted ethylenes as dipolarophiles for the 1,3‐dipolar cycloaddition reaction. The reactivities of electron‐withdrawing and ‐donating substituted ethylenes were examined by estimating their activation energies. The calculated activation energies predicted that the most reactive species is ( E )‐1,2‐C 2 H 2 (NO) 2 , whereas the least reactive is ( E )‐2‐butene. Namely, it was demonstrated that 16‐electron 1,3‐dipole reactants with more electropositive substituents in terminal positions and ethylenes that possess more strongly electron‐withdrawing substituents facilitate 1,3‐dipolar cycloaddition reactions. All of the theoretical results can be rationalized using the configuration mixing model. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 83: 318–323, 2001