Rhodium Catalyzed Conjugated Enones Participated Diels-Alder Reaction And Chemoselective Of Diazoesters Insertion Into The 4-Aminophenol

There’re two parts in this dissertation:Part Ⅰ:Rhodium(Ⅰ)-catalyzed Diels-Alder reaction between dienolsilyl ethers and 2-(1-alkyny l)-2-alken-1-ones.We have developed an unprecedented Diels-Alder cycloaddition of dienolsilyl ethers with 2-(1-alkynyl)-2-alken-l-ones in the presence of catalytic amount of Rh(NBD)2BF4,providing a facile access to synthetic multisubstitued cyclohexenes.This unprecedented process was explored during the course of testing our hypothesis that conjugated eneyne ketone compounds afforded a funanyl 1,3 dipole,which would react with dienolsilyl ethers to afford fused bicyclic funo[3,4-c]suberanes by[4+3]cycloaddition.Also,we have investigated the transformation of these cyclohexenes,which can transferred into bridged tricyclic cycloheptadienes under catalytic amount of gold.The salient features of this reaction include simple and easy accessible substrates,broad substrate scope,mild conditions,highly atom economy,environmentally benign.Part Ⅱ:Chemoselective insertion of aminophenols with diazo compounds.Our group has focused on the research of diazo compounds.We attempted to achieve the hypothesis that chemoselective insertion of aminophenols with diazo compounds:N-H insertion vs.O-H insertion.We tested a series of metal catalysts,ligands,addictives to address this issue.Unfortunately,we have not obtained satisfactory results.But,it’s noteworthy that the amount of caesium carbonate played an important role in switching from the N-H insertion products to the imine products.