Nitrogenation of Hydrocarbons via Transition-Metal and Non-Metal Catalysis

Abstract

The overall objective in the Nicholas Group's Amination Project is to develop new methodologies to form C-N bonds via C-H functionalization that utilize transition metal activation of non-polar and otherwise unreactive saturated and unsaturated hydrocarbons. Within this context, several new methodologies have been discovered and developed in the field of amination, and are presented within this document. For example, investigations aimed at the development of a mild allylic amination using nitroaromatics as N-source have resulted in a novel sodium borohydride and iron (II) phthalocyanine promoted reaction, the first example of microwave-assisted allylic amination, and a new Fe-Cu co-catalyst system that produces allylamine product in > 98% N-selectivity. In addition to allylic amination, we have developed a new iron (II) phthalocyanine catalyzed indolization of arylalkynes and N-aryhydroxylamines in order to form parent (NH) indoles efficiently in one-step. Several new indoles as well as some biologically relevant targets have been produced with this method. Finally, we have developed the first nontransition- metal-catalyzed aminosulfonation of hydrocarbons. In addition, we have discovered the first protic acid-catalyzed amidation as well as a novel I2-catalyzed nitrenoid C-H insertion of benzylic, tertiary, and secondary saturated hydrocarbons. During mechanistic investigations of the iodine-promoted reaction, a novel aminating agent was discovered that is stable at < 0oC and efficiently produces aminosulfonated hydrocarbons under remarkably mild conditions.