Organic nitrogen-containing compounds, including amines, are essential components of diverse biologically and pharmaceutically important molecules. One strategy for the introduction of nitrogen into substrates bearing multiple reactive bonds is the insertion of a monovalent nitrogen fragment (nitrene or nitrenoid) into a carbon-hydrogen (C-H) or direct addition to a carbon-carbon double bond (C=C). However, employing well-defined catalyst and ligand architectures to achieve predictable and chemoselective reagent control has been challenging due to the tendency for substrate control. We have developed a novel 'dynamic' approach to amination, where the perturbation of an equilibrium mixture of catalytic species formed from a single metal source (AgOTf) and a single ligand (phenanthroline) promotes either aziridination or C-H insertion in a variety of alkene and allene substrates. The chemoselectivity in this remarkable catalyst system is controlled by inducing changes in the coordination geometries of the active species in situ under operationally simple reaction conditions. The ability of Ag(I) complexes to readily adopt multiple coordination geometries has also led to new catalyst systems capable of promoting tunable intra- and intermolecular aminations, as well as enantioselective aminations, while opening a potential gateway for further extension of this concept to chemoselective C-C, C-O and C-X bond forming reactions. Application of this chemistry to the development of a unified, versatile strategy for the synthesis of complex amines will also be described.

Unified strategy for the construction of complex amines using "dynamic" silver catalysis

247th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.