Transition Metal-catalyzed Oxidative Annulations Of 2-Arylindoles With Quinone Derivatives

In this thesis,we successfully developed an efficient and practical procedure for the synthesis of 9H-dibenzo[a,c]carbazol-3-ols,indole-containing spirocyclic compounds,indolo[1,2-f]phenanthridines,and indole-containing bridged nine-membered cyclic compounds.The main results are as follows:First,we disclosed a novel and practial methodology for the preparation of 9H-dibenzo[a,c]carbazol-3-ols and new spirocyclic products by rhodium-catalyzed substrate-tunable oxidative annulation and spiroannulation reactions.Intriguingly,with 2-arylsubstituted indoles,benzoquinone could act as a C2 synthon to afford dibenzo[a,c]carbazoles.On the contrary,when 2-aryl-3-substituted indoles were used,benzoquinone switched to act as a C1 synthon to furnish spirocyclic compounds.Next,we developed an iridium-catalyzed oxidative [4+2] annulation reaction of 2-arylindoles using quinone derivatives as C2 synthons for the preparation of indolo[1,2-f]phenanthridine derivatives.In addition,we obtained diverse transformations of the phenanthridine derivatives,which showcase the synthetic potential of the present protocol.Finally,we also developed a rhodium-catalyzed oxidative [4+5] annulation reaction of 2-arylindoles with quinone monoacetals for the selective preparation of bridged nine-membered carbocyclic and heterocyclic compounds.When 2-aryl substituted indoles employed,this oxidative [4+5] annulation reaction affords bridged nine-membered carbocyclic compounds with excellent indolyl C3-selectivity.On the other hand,with 2-aryl-3-substituted indoles as the substrates,bridged nine-membered heterocyclic compounds are exclusively formed via oxidative N1-annulation.