Cobalt, Nickel and Rhodium Complexes as Catalyst: Synthesis of Indenamine, Indenone, Isoquinolone and Isoindolinone Derivatives Via a Annulation Methodology

• Main Authors: Liu, Chuan-Che, 劉全哲
• Other Authors: Cheng, Chien-Hong
• Format: Others
• Language: zh-TW
• Published: 2010
• Online Access: http://ndltd.ncl.edu.tw/handle/97231502589951488506

博士 === 國立清華大學 === 化學系 === 98 === In this thesis, we have demonstrated a series of cobalt, nickel and rhodium-catalyzed annulations and their application in organic synthesis are discussed in detail. The thesis is divided into five chapters. The first chapter explains the synthesis of indenamines, indene–enamines and indenones derivatives, the second chapter describes the preparation of indenoisoquinolinones derivatives, the third chapter describes the synthesis of indenones derivatives, the fourth and fifth chapter describes the synthesis of isoquinolone and isoindolinone derivatives. Chapter 1 : We have demonstrated a new three component methodology for the synthesis of substituted indenamines, indenimines and indenones via a cobalt-catalyzed three component reaction. The reaction is highly regioselective and various functionalized indenamine derivatives can be prepared. The interesting difference of products, regiochemistry and mechanisms from those of the previous nickel-catalyzed o-halobenzaldimines and alkynes that gave isoquinoline products is arisen from the different natural properties of 5-membered azametalcycles of cobalt and nickel. Chapter 2 : In the presence of [CoI2(dppf)] and ZnCl2, the methyl 2-(2-(trimethylsilyl)ethynyl)benzoate and its congeners undergo multiple bond forming reactions with o-halo-benzaldimines. To produce diverse kinds of indenoisoquinolinone derivatives in good to excellent yields. Further oxidation of these derivative using SeO2 results indenoisoquinolin-dione derivatives in excellent yields. Finally, as an application of these methods biologically active indenoisoquinolinone derivatives 2.28u and 2.19 were prepared in a very short fashion. Chapter 3 : We have demonstrated cobalt catalyzed two types of annulation reactions of o-(methoxycarbonyl)phenylboronic acid with propargyl alcohol or amide derivatives via the ligand tuning. The additional bidentate phosphine ligands gave regioselective formation of isochromanone, isoquinolinone and indenone derivatives in good to excellent yield. Chapter 4: We have demonstrated a easy and convenient nickel-catalyzed annulation reaction of substituted 2-halobenzamides with alkynes to give the corresponding isoquinolinone in good yields. The nickel-catalyzed annulation reactions of acrylate also proceeded smoothly to give isoindolinone derivatives in good yields. The present protocol is successfully applied to the total synthesis of oxyavicine with excellent yield. Chapter 5: We have successfully developed a new efficient rhodium catalyzed synthesis of substituted isoquinoline derivatives from the reaction of aromatic amides and alkynes. The transformation involves an rhodium-catalyzed C-H bond activations and C-C/C-N bond formations in one-pot. The present protocol is also successfully applied to synthesis of isoindolinone derivatives.