RESUMO
The first and asymmetric total syntheses of two C11-oxygenated hetisine-type diterpenoid alkaloids, namely, (+)-davisinol and (+)-18-benzoyldavisinol, is described. The concise synthetic approach features a HAT-initiated transannular redox radical cyclization, an ODI-Diels-Alder cycloaddition, and an acylative kinetic resolution. By incorporating an efficient late-stage assembly of the azabicycle, our strategy would streamline the synthetic design of C20-diterpenoid alkaloids and pave the way for their modular syntheses.
RESUMO
A bioinspired photo-Fries/imine capture cascade reaction was developed in continuous-flow mode, which facilitated the rapid construction of a series of diversely functionalized 2,7-heterocycle-fused tetrahydrocarbazoles, the ubiquitous core structures embedded in strychnos and akuammiline-type monoterpene indole alkaloids. The synthetic utility of this novel method has been preliminarily explored by the first total synthesis of (+)-alsmaphorazineâ C and formal synthesis of (+)-strictamine in a concise and efficient manner.