Studies On Synthesis Of Crinipellins

The total synthetic research of complex natural products has always been the focus and direction of efforts for synthetic chemists.It is particularly important that exquisite design and novel methods in efficiently completing specific molecules.In this paper,the synthesis of the diterpenoid natural product Crinipellins was studied based on the MHAT reaction and Ireland-Claisen rearrangement reaction as the key strategy,and the description mainly starts from the following three chapters.In Chapter 1,we traced the history of MHAT reaction,and comprehensive overview of the achievements of MHAT reaction in constructing C–X bond and C–C bond.Meanwhile,we investigated the research progress of MHAT mediated radical addition reaction between alkenes and cyano groups,and summarized its application in total synthesis of natural products.In Chapter 2,we reviewed the isolation,structural identification,and biological activity of crinipellins.Subsequently,we have systematically reviewed all the total synthesis works since the separation of crinipellins.In Chapter 3,we mainly introduce our group’s research on the synthesis of crinipellins,and this chapter is the core part of the paper.Firstly,we started from the simulated substrate,and made a simple trials of Ireland-Claisen rearrangement reaction and MHAT reaction.Subsequently,during the research process of the target molecule,we have successfully constructed three consecutive all-carbon quaternary carbons through uninterrupted exploration and adjustment.Thirdly,we obtained the precursor of Stetter reaction through a series of transformations.At the same time,with the aim of simplifying synthetic route and facilitating the preparation of materials,we have further adjusted and optimized the synthesis of key intermediates.