Theoretical Study of NCO and RCCH (R = H, CH3, F, Cl, CN) [3 + 2] Cycloaddition Reactions

Hsin Tsung Chen, Jia Jen Ho*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)


We carried out a theoretical study of the radical [3 + 2] cycloaddition reaction of NCO + RCCH (R = H, CH3, F, Cl, CN), which produced a five-membered ring heterocyclic oxazole. An asynchronous two-bond formation mechanism was found, which led to a certain regioselectivity in the products when the substituted alkyne was used as a reactant. The preferable reactive sites of RCCH in various substituents are calculated by employing the Fukui functions and HSAB theory, and the results are in good agreement (except R = F) with the calculated energy barriers of the transition states in the potential energy surfaces. The N atom of NCO attacks the unsubstituted carbon atom of RCCH first, followed by the ring closure of the O atom with the other carbon atom to form the substituted oxazole. The order of the calculated first transition barriers (uts1) in the substituted alkynes (RCCH) is R = H > F > CN > Cl > CH3 and that for the second transition barriers (uts2), R = H > CH3 > CN > Cl > F. The reason for the decreased transition barriers of the substituted alkynes is analyzed.

Original languageEnglish
Pages (from-to)7643-7649
Number of pages7
JournalJournal of Physical Chemistry A
Issue number38
Publication statusPublished - 2003 Sept 25

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


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