| In the past forty years,the development of organic synthesis and free radical chemistry has crossed and the field of modern free radical reactions in organic synthesis has emerged.Free radicals with fast addition/elimination rates can be used as catalysts for a series of free radical reactions in which the free radicals(X·)are catalysts and their precursors(usually HX)are catalytic precursors.Although there have not been many reports on such reactions,they have broad development prospects and have been applied to the synthesis of natural products.Some asymmetric reactions have also been developed.In this paper,the free radical rearrangement reaction of N-(2-ethynylaryl)arylamide catalyzed by NHC-boryl radical was developed.The reaction mechanism was proposed and the mechanism was calculated and discussed in detail.The first chapter of the thesis expounds the relationship between free radical chain reaction and free radical catalytic reaction,including the intrinsic cycle of free radical chain reaction from perspectives of initiation,inhibitor and side reaction.The catalytic process and free radical catalysis involved in the radical reaction were classified and summarized.The second chapter of the thesis introduces the free radical rearrangement reaction of N-(2-ethynylaryl)arylamide catalyzed by NHC-boryl radicals.Based on some unique reaction properties of NHC-boryl radicals and previous work,we designed N-(2-ethynylphenyl)benzamide as substrate and found that NHC-boryl radical can catalyze this kind of substrate for the intramolecular rearrangement reaction to obtain quinolinone derivatives.This reaction realized the catalysis of NHC-boryl radical for the first time.Based on the differences in the reaction properties of sulfur radicals and NHC-boryl radicals,a preparation method of an anthrone compound containing a sulfide ether group was developed.The reaction mechanism was explored in detail by DFT calculation. |
PDF Full Text Request