This grant in the Organic and Macromolecular Chemistry Program supports research on metal-catalyzed chemical reactions which involve transient intermediates known as carbenoids. Prof. Doyle's work is aimed at developing new reagents and catalysts which can significantly enhance selectivity in such processes.Since carbenoids are a widely occurring family of reaction intermediates which can be used for constructing a variety of organic chemical types, most notably strained three-membered rings, this work has important applications to chemical synthesis. In this project several approaches are taken to enhance selectivity in catalyzed carbenoid reactions, including synthesis of diazocarbonyl reagents with restricted access to the diazo functionality, the design of new and effective catalysts for selective carbenoid transformations, and substrate constructions that are formulated to provide control over competing reaction pathways.