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

Xiaolin Yue; Qingyang Zhou; K N Houk

doi:10.1021/acs.joc.3c00993

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

J Org Chem. 2023 Oct 20;88(20):14303-14307. doi: 10.1021/acs.joc.3c00993. Epub 2023 Sep 28.

Authors

Xiaolin Yue^{1

2}, Qingyang Zhou³, K N Houk³

Affiliations

¹ School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China.
² College of Chemistry, Nankai University, Tianjin 300071, China.
³ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.

PMID: 37768874
DOI: 10.1021/acs.joc.3c00993

Abstract

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.