Palladium/Norbornene Co-Catalyzed Functional Group Of In Situ C-O And Ortho C-H Bonds Of Aryl Triflates

The Catellani reaction can form multiple chemical bonds in a single step,making it highly advantageous for synthesizing multi-substituted aryl compounds and cyclic compounds.This makes it an essential process for organic synthesis.However,the use of toxic and pre-prepared aryl iodine compounds often restricts its applicability.In this study,the functionalization of both the standard C-O bond and ortho C-H bond in phenol trifluoromesylate was achieved through a one-step Catellani reaction strategy utilizing said substrate.The successful implementation of this project will not only promote greener practices within Catellani reactions but also expand their application range within organic synthesis.The specific research content and results are detailed below:1.Preparation of aromatic tertiary amines via Pd/Norbornene co-catalyzed standard C-O bond enylation and ortho-C-H bond amination of aryl trifluoromethanesulfonate:After screening various palladium compounds,norbornene derivatives,ligands,bases,solvents,temperatures and reaction times among other conditions,the optimal reaction conditions were ultimately determined.These conditions proved adaptable for aryl trifluoromethanesulfonate as well as terminal olefin nucleophiles and amine electrophiles resulting in the synthesis of a range of o-alkenyl tertiary anilines with yields ranging from good to excellent.This reaction represents a new aryl C-O bond transformation mode,which extends the range of Catellani type reactions and improves the application value of phenol compounds in organic synthesis.Gram scale up reaction further proves the potential application value of this system.2.Preparation of aromatic ketones by Pd/Norbornene co-catalyzed alkylation of standard C-O bonds and acylation of ortho C-H bonds of aryl trifluoromesulfonate: An online strategy for activating carboxylic acid compounds to provide acyl sources is proposed to achieve the acylation of aryl trifluoromesylate ester’s C-H bond,resulting in the synthesis of aromatic ketones.Subsequently,a series of conditions will be employed to screen the reaction and obtain optimal reaction conditions that enable substrate expansion.In conclusion,this paper presents the preparation of aromatic tertiary amines and aromatic ketones through palladium/norbornene co-catalyzed alkylation of the standard C-O bond and amination and acylation of the ortho-C-H bond of aryl trifluoromethanesulfonate.This work provides valuable insights into the utilization of phenol derivatives and promotes greener processes for Catellani reaction.