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.