Tuning of α-Silyl Carbocation Reactivity into Enone Transposition: Application to the Synthesis of Peribysin D, <i>E</i>-Volkendousin, and <i>E</i>-Guggulsterone
Paresh R. Athawale, Vishal M. Zade, Gamidi Rama Krishna, D. Srinivasa Reddy
Abstract
A reliable method for enone transposition has been developed with the help of silyl group masking. Enantio-switching, substituent shuffling, and Z-selectivity are the highlights of the method. The developed method was applied for the first total synthesis of peribysin D along with its structural revision. Formal synthesis of E-guggulsterone and E-volkendousin was also claimed using a short sequence.
Topics & Concepts
ChemistrySilylationEnoneTransposition (logic)SubstituentStereochemistrySelectivitySequence (biology)Masking (illustration)Organic chemistryLiteratureComputer scienceBiochemistryArtArtificial intelligenceCatalysisPharmacological Effects of Medicinal PlantsNatural product bioactivities and synthesisPlant biochemistry and biosynthesis