Publication Date:
2012-04-15
Description:
A theoretical study on the regioselectivity of 1,3-dipolar cycloaddition reaction between an uncommon dipole (thiocarbonyl S -imide) with cyclopent-3-ene-1,2-dione (DPh1) and methoxyethene (DPh2) has been carried out by means of several theoretical approaches, namely, activation energy, Houk's rule based on the frontier molecular orbital theory and density functional theory (DFT) reactivity indices. The calculations were performed at the DFT-B3LYP/6-31G(d) level of theory using GAUSSIAN 09. The present analysis shows that the 1,3-dipolar cycloaddition of thiocarbonyl S -imide with DPh1 and DPh2 has normal-electron demand and inverse-electron demand character, respectively. Moreover, the results obtained from energetic point view are in agreement with electronic approaches, and the Houk's rule is capable to predict true regioselectivity. Copyright © 2012 John Wiley & Sons, Ltd. 1,3-Dipolar cycloaddition of thiocarbonyl S-imide with cyclopent-3-ene-1,2-dione and methoxyethene has normal-electron demand and inverse-electron demand character, respectively. The results of activation energies, frontier molecular orbital energies, Gazquez-Mendez rule, Chattaraj's polar model and Houk's rule for prediction of favored regioisomers are in agreement with each other.
Print ISSN:
0894-3230
Electronic ISSN:
1099-1395
Topics:
Chemistry and Pharmacology
,
Physics
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