This project is directed toward the discovery of new methods for the selective derivatization of alkynes. First-row transition metals will be evaluated for their ability to catalyze the addition of organometallic reagents to propargylic alcohols and amines. Trapping the vinyl organometallic intermediate will enable the synthesis of tetrasubstituted olefins. Carbometalation of terminal alkynes followed by trapping with an electrophilic oxygen or nitrogen donor will yield branched carbonyl derivatives with complete control of stereochemistry. With terminal alkyne substrates, the transformation generates aldehyde derivatives (enol esters). Further explorations will seek to develop tandem carbometalation / oxygenation of internal alkynes. Additionally, tandem carbometalation / amination will be developed to facilitate the synthesis of stereodefined enamines. Finally, the reactivity of the products of the tandem carbometalation/oxygenation will be evaluated in the context of a variety of enantioselective transformations, including asymmetric epoxidation, dihydroxylation and aminohydroxylation. A variety of educational programs will also be initiated, including a mentorship program for student researchers and a program to encourage the participation of undergraduate and high school students in active laboratory research.
With the support of this CAREER award from the Organic and Macromolecular Chemistry Program, Professor Joseph Ready, of the Department of Biochemistry at the University of Texas Southwestern Medical Center at Dallas, is developing new reactions applicable to the synthesis of complex organic molecules. The proposed research explores fundamental aspects of synthetic chemistry, including the creation of carbon-carbon, carbon-oxygen and carbon-nitrogen bonds. The objectives of these undertakings are twofold. First, an increased understanding of catalysis, oxidation and transition metal chemistry is sought. Secondly, access to valuable materials is anticipated. The proposed research involves the development of new chemical reactions and an exploration of the synthetic potential of the newly-accessible materials. Substantial preliminary data attests to the likelihood that these endeavors will find success, and that broadly applicable methods and understanding will emerge. Professor Ready will also develop a set of programs designed to encourage active involvement in research and to foster success in student research through mentorship.
