Competing nature of intramolecular [4 + 2] and [3 + 2] cycloaddition reactions: a theoretical study Full article
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Journal of Physical Organic Chemistry
ISSN: 0894-3230 , E-ISSN: 1099-1395 |
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| Output data | Year: 2003, Volume: 16, Number: 4, Pages: 253-263 Pages count : 11 DOI: 10.1002/poc.613 | ||
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Abstract:
Comparative study of the intramolecular alkyne triple bond addition reaction to the conjugated C≡C—CHX moiety (X = CH2,O,S,NH) revealed that two different pathways are possible in the system, namely [4 + 2] and [3 + 2] cycloaddition reactions. The energetically preferred pathway for enynes (X = CH2) involves [4 + 2] cycloaddition leading to benzene derivatives, whereas heteroatom-substituted substrates undergo [3 + 2] cycloaddition resulting in an five-membered aromatic ring in the final product. This paper reports a detailed mechanistic study based on full potential energy surface calculations at the MP2 and B3LYP theory levels, with MP4(SDTQ) energy evaluation. The effect of solvent was included within the PCM approach. Copyright © 2003 John Wiley & Sons, Ltd.
Cite:
Ananikov V.P.
Competing nature of intramolecular [4 + 2] and [3 + 2] cycloaddition reactions: a theoretical study
Journal of Physical Organic Chemistry. 2003. V.16. N4. P.253-263. DOI: 10.1002/poc.613 Scopus OpenAlex
Competing nature of intramolecular [4 + 2] and [3 + 2] cycloaddition reactions: a theoretical study
Journal of Physical Organic Chemistry. 2003. V.16. N4. P.253-263. DOI: 10.1002/poc.613 Scopus OpenAlex
Identifiers:
| Scopus: | 2-s2.0-0037389537 |
| OpenAlex: | W2167124429 |