Computational Exploration of the Thermal Rearrangement of Basketene: One Forbidden versus Two Allowed Pericyclic Reactions

Computational Exploration of the Thermal Rearrangement of Basketene: One Forbidden versus Two Allowed Pericyclic Reactions

The thermal rearrangement of basketene to Nenitzescu’s hydrocarbon has been explored using density functional theory (M06-2X and ωB97X-D) and DLPNO–CCSD­(T) quantum mechanics. Both the sequential thermally allowed retro Diels–Alder followed by Cope rearrangement and the thermally forbidden retro-[2...

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Veröffentlicht in:Journal of organic chemistry 2023-10, Vol.88 (20), p.14303-14307
Hauptverfasser: Yue, Xiaolin, Zhou, Qingyang, Houk, K. N.
Format: Artikel
Sprache:eng
Schlagworte:
cycloaddition reactions
density functional theory
organic chemistry
quantum mechanics
thermodynamics
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Zusammenfassung:The thermal rearrangement of basketene to Nenitzescu’s hydrocarbon has been explored using density functional theory (M06-2X and ωB97X-D) and DLPNO–CCSD­(T) quantum mechanics. Both the sequential thermally allowed retro Diels–Alder followed by Cope rearrangement and the thermally forbidden retro-[2 + 2] cycloaddition were studied. The controlling role of orbital symmetry rather than reaction thermodynamics is demonstrated.
ISSN:0022-3263
1520-6904
1520-6904
DOI:10.1021/acs.joc.3c00993