Recent advances in copper- and palladium-catalyzed carbon-heteroatom and carbon-carbon bond-formation

Abstract

Metal-catalyzed nucleophilic substitution reactions of aryl halides have become one of the most valuable and useful classes of reactions developed in the last 30 years. Foremost among these processes are the classes of palladium- and copper-catalyzed reactions, which employ heteroatom-based nucleophiles. Herein, newly designed catalyst systems are presented for the palladium- and/or copper-catalyzed nucleophilic substitution reactions of aryl halides with a variety of nucleophiles, including (benz)imidazoles, oxindoles, 2-, 3- and 4-hydroxypyridines, anilines, and aliphatic, benzylic, allylic and propargylic alcohols. In many cases, catalyst optimization and ligand structure are discussed and evaluated. Where applicable, the palladiumand copper-based catalyst systems are contrasted to demonstrate the complementary relationships between the employment of these two metals. Chapter One Chapter Two Chapter Three Chapter Four Chapter Five. Palladium- and Copper-catalyzed Reactions of Imidazoles and Benzimidazoles with Aryl Halides. Orthogonal Selectivity in Copper- and Palladium-catalyzed Reactions of Aryl Halides with Oxindoles. Copper-catalyzed Reactions of Hydroxypyridines and Related Compounds with Aryl Halides. Pyrrole-2-carboxylic Acid as a Ligand for the Copper-catalyzed Reactions of Primary Anilines with Aryl Halides. An Improved Copper-based Catalyst System for the Reactions of Aryl Halides with Aliphatic Alcohols.