Total Syntheses of Rhodomollins A and B
Weizhao Zhao, Duo Zhang, Yuran Wang, Ming Yang
Abstract
The first and asymmetric total syntheses of rhodomollins A and B, two rhodomollane type grayanoids featuring a d -homograyanane carbon skeleton and an oxa -bicyclo[3.2.1] core, were accomplished via a convergent strategy. A Stille coupling and a lithium-halogen exchange/intramolecular nucleophilic addition to the aldehyde sequence were employed to assemble two enantioenriched fragments. The oxa -bicyclo[3.2.1] core was achieved through an intramolecular S N 2 substitution of cyclic sulfate of 1,2-diols (Williamson ether synthesis). The A ring oxidation states were adjusted by a Payne/Meinwald rearrangement sequence and subsequent redox transformations.
Topics & Concepts
ChemistryIntramolecular forceStille reactionBicyclic moleculeSN2 reactionStereochemistryTotal synthesisRing (chemistry)Nucleophilic substitutionNucleophileEtherAldehydeMedicinal chemistryOrganic chemistryCatalysisPolymerBioactive Natural Diterpenoids ResearchMarine Sponges and Natural ProductsTraditional and Medicinal Uses of Annonaceae