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A Thermodynamic and Kinetic Insight into the Pathways Leading to a Highly Functionalized Ketenimine: A Computational Study
Author(s) -
Darijani Mahdieh,
HabibiKhorassani Sayyed Mostafa,
Shahraki Mehdi
Publication year - 2015
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20946
Subject(s) - ketenimine , chemistry , isocyanide , kinetic energy , transition state , computational chemistry , reaction coordinate , kinetics , chemical shift , reaction mechanism , thermodynamics , stereochemistry , organic chemistry , catalysis , physics , quantum mechanics
ABSTRACT All steps of two mechanistic pathways for the synthesized ketenimine through a multicomponent reaction between cyclohexyl isocyanide 1 and acetylen ester 2 in the presence of CH‐acid 3 have been thermodynamically and kinetically evaluated. Intrinsic reaction coordinate calculations were performed for the optimized structures to verify the connectivity of all transition states with reactants and products. The kinetic data showed that the step 1 of the two proposed mechanisms was a rate‐determining step. Also, activation (Δ G ‡ , Δ H ‡ , Δ S ‡ ) and thermodynamic (Δ G °, Δ H °, Δ S °) parameters confirmed that the second mechanism for generation product 4b was favored energetically. In addition, the single‐point 1 H and 13 C NMR (GIAO) chemical shift calculations showed that the product obtained from the approval pathway was according to the experimental data.