Inverse Electron-Demanding Diels-Alder Reactions in the Chemical Synthesis of Prenylated Indole Alkaloids Containing a Bicycle[2.2.2]diazaoctane Moiety: A Theoretical Study.

Autor: Xu W; Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, P. R. China.; Institute of Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, 518132, P. R. China., Sun TY; Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, P. R. China.; Institute of Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, 518132, P. R. China., Di Y; State Key Laboratory of Phytochemistry and, Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, 650201, P. R. China., Hao X; State Key Laboratory of Phytochemistry and, Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, 650201, P. R. China., Wu YD; Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, P. R. China.; Institute of Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, 518132, P. R. China.; College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.
Jazyk: angličtina
Zdroj: Chemistry, an Asian journal [Chem Asian J] 2023 Apr 03; Vol. 18 (7), pp. e202300063. Date of Electronic Publication: 2023 Mar 01.
DOI: 10.1002/asia.202300063
Abstrakt: The Diels-Alder reaction is believed to be a key step in the biosynthesis of prenylated indole alkaloids containing a bicycle[2.2.2]diazaoctane moiety. Many chemical syntheses of bicyclic structures by Diels-Alder reactions have been reported, but the reaction mechanism remains underexplored. We have carried out DFT calculations on both acid- and base-promoted Diels-Alder reactions in these syntheses and reveal that the reactions occur through an inverse-electron demand mechanism. We hope that the new mechanism is helpful for the mechanistic understanding of the biosynthesis of this class of important natural products.
(© 2023 Wiley-VCH GmbH.)
Databáze: MEDLINE
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