Palladium-Catalyzed Amination Of Aryl Halides With Alicyclic Amines Or Aryl Amines

This dissertation aims to develop high active palladium catalyst system for the amination of aryl bromides and aryl chlorides.In part one, PdCl2/PPh3 was acted as catalyst for the amination of aryl bromides with morpholine or piperidine at the present of t-BuONa in refluxing toluene, and excellent iso-lated yields were obtained. The advantages of this catalyst system include simple reaction system, high yield, easy operation and potential application significance.In part two, an efficient catalyst system consisting of substituted salicylaldimines, PPh3 and Pd(PPh3)2Cl2 was developed for the amination reaction after screening a series of salicylaldiminato ligands. This catalyst system can even catalyze the amination of unactive aryl chlorides with aryl amines at the present of t-BuONa and sodium pivalate in refluxing o-xylene in high yields. It is the first time that salicylaldimine was used as ligand to the amination of unactive aryl chlorides. This reaction has certain technical and practical significance.In part three, based on the result of the previous part, further research was done for the one-pot amination of aryl bromides with aryl primary amines to synthesize triarylamines and desired products were obtained in high yields. The advantages of the reaction are convenient operation and low cost.In part four, a reactivity intermediate of the above catalyst system consisting of substituted salicylaldimine and PPh3 was captured. X-ray crystallography showed the structure of this reactivity intermediate, in which PPh3 and salicylaldimine complex with palladium center together. Then a proposal mechanism was suggested for this palladium-catalyzed amination.