Investigations of an Unexpected [2+2] Photocycloaddition in the Synthesis of (-)-Scabrolide A from Quantum Mechanics Calculations.

Autor: Zhang T; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States., Cusumano AQ; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States., Hafeman NJ; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States., Loskot SA; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States., Reimann CE; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States., Virgil SC; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States., Goddard WA 3rd; Materials and Process Simulation Center, Beckman Institute, California Institute of Technology, Pasadena, California 91125, United States., Stoltz BM; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Jazyk: angličtina
Zdroj: The Journal of organic chemistry [J Org Chem] 2022 Nov 04; Vol. 87 (21), pp. 14115-14124. Date of Electronic Publication: 2022 Oct 21.
DOI: 10.1021/acs.joc.2c01693
Abstrakt: We utilize ab initio quantum mechanics calculations to evaluate a range of plausible mechanistic pathways for the unexpected formation of a [6-4-4] ring system from an enone-olefin photocycloaddition in the synthesis of (-)-scabrolide A, previously reported by our group. We present a mechanistic analysis that is consistent with all current experimental observations, including the photoexcitation, the C-C bond formation, and the associated chemo- and diastereoselectivity.
Databáze: MEDLINE