The Studies Of Pd-catalysed C-H Activation/Annulation Reaction For The Preparation Of Isoquinolinones And Isoquinoline N-oxides

Transition metal-catalysed direct formation of C-C or C-X (X=heteroatom)chemical bond via C-H activation pathway represents an important andatom-economic strategy to construct complex structures which has importantscientific value in both pharmaceutical industry and material sciences. The research ofC-H activation/annulation reaction has drawn great attention in organic synthesis. Inthe last several years, a considerable number of well-established C-Hactivation/annulation approaches have been developed for the synthesis of condensedheterocycles such as indole, benzofuran, isobenzofuranone, isocoumarin andisoquinoline. As less-expensive metal compared with Rhodium and Ruthenium,Palladium catalysts are widely used in the synthesis of various heterocycles.This thesis consists of two parts. In the first part, a novel method on palladiumcatalysed synthesis of N-aryl isoquinolinones has been demonstrated, N-arylbenzamide and internal alkyne were used as starting materials, NaBr and KOH asadditives, CuCl2H2O as oxidative, the reaction was carried out in DMF at120oC.Under the conditions above, a series of N-aryl isoquinolinones were obtained in goodyields with good regioselectivity. The structure of compounds were fully characterized.In the second part, we have introduced the selective formation of isoquinoline N-oxideunder palladium-catalysed oxime-directed C-H activation/annulation reaction. Oximeand internal alkyne were used as starting materials, ZnBr2and catalytic TFA asadditives, the reaction was carried out in PhCl: dioxane=2:1at120oC. Under theseconditions, a series of isoquinoline N-oxide were obtained in good yields with goodregioselectivity. The novel compounds were fully characterized by1H,13C NMRspectroscopy and HEMS spectrometry. While we have introduced a two step-one potmethod for the synthesis of isoquinoline analogues.