47137-G1
New Catalysts for Asymmetric Intermolecular C-H Amination
Our research conducted with financial assistance from the Petroleum Research Fund has resulted in the discovery of a catalyst system that allows highly enantioselective amination of benzylic and allylic C–H bonds. This system utilizes a novel ruthenium(II) catalyst, distinguishing it from rhodium-based catalysts that have been explored by other researchers. The results of this research were communicated in Angewandte Chemie, Int. Ed. earlier this year (Milczek, E.; Boudet, N.; Blakey, S. Angew. Chem., Int. Ed. 2008, 47, 6825). Although we have not discovered a catalyst system for directed intermolecular C–H amination, our research in the area of metallonitrene chemistry has lead to the discovery of a powerful new metallonitrene/alkyne metathesis cascade. This reaction allows particularly simple acyclic molecules containing both an alkyne and a tethered sulfamate ester to be converted to highly functionalized, complex polycyclic alkaloid structures in a single transformation. A preliminary communication describing this work was published in the Journal of the American Chemical Society earlier this year (Thornton, A. R.; Blakey, S. B. J. Am. Chem. Soc. 2008, 130, 5020). Continuing research in our laboratory focuses on utilizing metallonitrenes as reactive intermediates for the controlled functionalization of simple hydrocarbon substrates.
