Professor Maitland Jones, Jr. is supported by the Organic Dynamics Program for his studies of reactive intermediates. Professor Jones, of the Department of Chemistry at Princeton University, uses hydrocarbon-based precursors to carbenes in order to avoid interference in subsequent chemistry by the more-commonly used nitrogen-based carbene precursors and to assess the importance of such precursor chemistry in previously studied reactions. Formation of sterically-stabilized bridgehead alkenes through the ring expansion of 1-norbornylcarbenes and carbene interconversions via `zipper` mechanisms are also under investigation. Analogous zipper reactions of carboranylcarbenes will be explored as a rational route for the synthesis of silicon-containing carboranes, and mechanistic and synthetic studies will be carried out for 1,2-dehydro-o-carborane. Professor Maitland Jones, Jr., of the Department of Chemistry at Princeton University, with the support of the Organic Dynamics Program, studies the formation and chemistry of highly reactive compounds known as carbenes. These compounds contain a central carbon atom to which only two bonds to other atoms are present, in contrast to the more commonly found four bonds. Although carbenes have been studied for some time, it has recently been determined that many of the reactions claimed to lead to their formation in fact do not give rise to simple carbenes but rather to materials still incorporating portions of their precursor molecules. Professor Jones has developed a synthetic route which provides for the unambiguous formation of carbenes and allows the exploration of their reaction chemistry unencumbered by the complications of precursor chemistry. Given their instability, carbenes often form relatively high-energy products, including molecules displaying patterns of chemical bonds often assumed to be impossible to obtain. These studies advance our fundamental understanding of carbenes as reactive intermediates, adding to our understanding and potential control of a wide variety of significant chemical transformations.
