Copper-catalyzed Amidation Of Arylboronic Acids And Regioselective C-H Sulfonyloxylation Of Electron-rich Arenes

Transition metal-catalyzed C-N coupling reaction has been developed,a variety of methods for the synthesis of N-arylamides were emerged.By contrast,the amidation reactions of aryl halides have a great challenge because of all of the halogens are tolerant.And the amidation reactions of simple arenes remain some shortcomings,for example,low reactivity,low selectivity and electron-deficient arenes could not undergo this reaction.Developing the efficient,controllable,and green synthesis method has a great significance in a variety of drug molecules and biologically active molecules.For the more,Regioselective C-H oxygenation of arenes has become a current research focus.One of the biggest challenges in this field is C-H activition and regioselective control of C-H oxygenation.Para-selective C-H oxygenation of amides,sulfonamides or phenols was achieved,but this strategy can only be applicable to the specific substrates,such as amides,phenols and their analogues.C-H oxygenation of simple arenes has been developed with low selectivity in several years.After years of effort,a variety of metal-catalyzed chelate-assisted regioselective C-H oxygenation of arenes have been developed greatly.Despite the tremendous advance,the corresponding arenes need additional functionalization,and its application was limited.The main contents of this paper are as follows:In the first chapter,A copper-catalyzed amidation of arylboronic acids with nitriles has been developed.In this reaction,both electron-rich and electron-deficient arylboronic acids can smoothly undergo this transformation.Furthermore,all of the halogens are tolerant.This reaction provides an efficient and complement methodology for the synthesis of various N-arylamides with a broad substrate scope.In the second chapter,we developed a copper catalyzed regioselective C-H sulfonyloxylation of electron-rich arenes with p-toluenesulfonic acid.Both steric and electronic effects are utilized to control the regioselective selectivity.In addition,The formed aryl sulfonates can be converted to phenols,as well as used as good partners of cross-coupling reactions.In conclusion,we developed a new synthesis method of N-arylamides.With improving its functional group compatibility,a variety of substituted aryl amides were synthesized efficiently according to this method.And it will be the basis of further efficient synthesis.Besides,we developed an efficient and controllable regioselective C-H sulfonyloxylation of electron-rich arenes to solve the low selectivity of C-H oxygenation of simple arenes.