Direacting-Group-Controlled Ring-Opening Addition And Hydroarylation Of Benzonorbrorndienes With Arenes Via C–H Activation

There has become a prominent method for the construction of new C-C bonds that the direct functionalization of C-H bonds in organic synthesis.The regioselectivity in C-H bond functionalization is now considered to be an economical synthesis tool of atoms and steps,because this conversion does not require pre-functionalization.There has become a straightforward method constructe C-C and C-X bonds by the transition-metal-catalyzed C-H bond functionalization with different directing groups.And to the synthesis of highly functionalized ketones,the weakly coordinating ketone-directed ortho C-H bond functionalization reactions is an efficient and straightforward method.Low coordinating carboxylates have also been successfully used as directing groups.The application of carboxylate as DG is intereated because there is carboxylate broadly abundant and can be removed tracelessly or used for further functionalization/derivatization.We have reported the Rh（Ⅲ）-catalyzed ring-opening addition of azabenzonorbornadienes with cyclic N-sulfonyl ketimines through C-H bond functionalization.It is reported the Rh-catalyzed ring-opening addition and hydroarylation of bicyclic alkenes through ortho C-H activation controlled by weakly coordinating directing groups ketone and carboxylate groups in order to further study the Rh-catalyzed system and the hydrocarbon functionalization with the oxa/azabenzobornene in this acticle.Through optimization of the conditions,the reaction catalyst system of[Rh Cp*Cl₂]₂,Ag NTf₂,Na OAc,1,2-dichloroethane was successfully established.In ketone-directed addition reaction,the stereoselective ring-opening C-H addition products were obtained in 34%-82%yields by via C-H bond functionalization at the ortho-position of the arenes.Without the expensive silver salt,both oxa-and aza-bicylic alkenes with different substituents participated under the developed reaction conditions.And there were the 1:2 addition products obtained in good to excellent yields,showing a wide range of functional group tolerance in the carboxylate-directed C-H bond functionalization reaction,and offering a synthetic method for the construction of highly substituted polycyclic organic compounds.And benzoic acid with substituents at the ortho-and meta-positions with azabenzobornene,and the reaction yields a 1:1 addition product with a good to excellent yield,showing good regioselectivity. The Rh-catalyzed ring-opening addition and hydroarylation of bicyclic alkenes through ortho C-H activation controlled by weakly coordinating directing groups ketone and carboxylate groups provide possible methods to synthesize biologically active compounds with different functional groups.It also provides theoretical research for the functionalization of C-H bonds.