Total Synthesis Of Epidithiodiketopiperazines Natural Products Epcoccin G And Amaryllidaceae Alkaloid (+)-?-Lycorane

Hydroindole alkaloids(such as: Epidithiodiketopiperazines natural products,Stemona Alkaloids,Catharanthus,Amaryllidaceae Alkaloids)are important components of natural alkaloids.How to efficiently synthesize the skeleton and apply it to the total synthesis of alkaloids is a problem.In this paper,we will introduce a asymmetric synthetic strategy for construting hydroindole skeleton and it's application in the asymmetric total synthesis of epicoccin G and(+)-?-lycorane.(1)Asymmetric Total Synthesis of Epidithiodiketopiperazines Natural Products Epicoccin GWe construted the hydrogenated indole skeleton by the intermolecular inverse-electron-demand [4+2] cycloaddition reaction and obtainned the hydrogenated indole skeleton with high efficiency and gram-scale.the chirality on the hydrogenated indole skeleton were induced by amino acid chirality.After,the oxidized state and framework of ETP monomer were adjusted by photocatalytic oxidation and Pd/C catalytic hydrogenation.Finally,asymmetric synthesis of the epicoccin core was achieved by a one-step condensation.The asymmetric total synthesis of epicoccin G was accomplished by a efficient 10 steps synthetic route.In addition,we prepared the epicoccin core in gram-scale,which provides good technical support for the subsequent large-scale production of ETP(Epidithiodiketopiperazines)alkaloids and the study of their structure-activity relationships.(2)Asymmetric Total Synthesis of Amaryllidaceae Alkaloid(+)-?-LycoraneAfter completing the asymmetric total synthesis of epicoccin G,the asymmetric total synthesis of(+)-?-lycorane was completed in six steps from the starting material,which is the intermediate for total synthesis of epicoccin G.This method is efficientive and provides a new synthetic strategy for future research on Amaryllidaceae Alkaloids.