Research On The Construction Of Dihydrocyclohepta[b]indoles And Macrocyclic Alkynes Via Catalytic Buchner Reaction Of Metal Carbencs

Metal carbene,due to its high reactivity,has diversified chemical transformation with various nucleophiles.It is an important intermediate for the construction of the C-C、C-X and complex molecular skeletons in orangic synthesis.Buchner reaction is one of the oldest and well studied reactions,in which,the carbene reacts with the arene,and efficiently construct the seven-membered rings,inculding polyocyclic fused heterocycle and marcocycle structure compatible with mulit-functional group.This thesis mainly studies on the Buchner reaction of alkyne embodied diazoacetates.By design of the substrate and regulation of the catalysts,dihydrocyclohepta[b]indoles and marcocyclic alkynes with broad functional group could be obtained selectively via the carbene/alkyne metathesis-Buchner reaction cascade process and direct Buchner reaction,respectively.The first chapter mainly summarized the reseach on diversified metal carbene reactions,including the Buchner reaction.And we put forward the specific research mentality and project.In the second chapter,we studies on the Buchner reaction of Cu-catalyzed construction of dihydrocyclohepta[b]indoles derivatives.This is the first example of Cu-catalyzed Buchner reaction of donor/donor type metal carbene which is generated in situ via the carbene/alkyne metathesis.In addition,the resulting dihydrocyclohepta[b]indoles skeleton is an important component of the nature prouducts and pharmaceutical molecules.The carbene/alkyne metathesis(CAM)terminated by the Buchner reaction is a step-economic approach with multiple C-C bonds formation in one reaction.The third chapter describes the direct Rh-catalyzed Buchner reaction for the synthesis of marcocyclic alkynes.This method via the metal carbene reaction,provides a direct and efficient methodology for the selectively construction of marcocyclic alkyne frameworks with multi-functional group compatibility under the mild reaction conditions.This method provides a new access to the synthesis of marcocyclic alkynes with structural diversity.