Metal-Catalyzed Silylene Transfer Reactions as Methods for the Synthesis of Strained trans-Cycloalkenes

New York University, New York NY

Investigators

Abstract

In this project, funded by the Chemical Synthesis Program, Professor Keith Woerpel of New York University develops new chemical reactions of silicon-containing reactive intermediates to synthesize a class of compounds, trans-cycloalkenes, that have been particularly difficult to prepare, and explores the chemistry of this class. The source of that difficulty has been their extraordinarily high energy, which renders them very reactive and difficult to isolate using conventional methods. Conversely, their distinctive reactivity makes these tempting intermediates for the synthesis of biologically active and other useful compounds. Once the reactivity of this particular type of compound has been determined, the structure and reactivity of structurally related compounds can be predicted, and the design and synthesis of pharmaceutical agents, of tools for exploring biological systems, of plastics for use in medical and technological applications, and of materials for solar cells can be exploited. This project also serves as a training tool for graduate, undergraduate, and precollege students to prepare themselves for careers in research, in medicine, and in materials science. Divalent silicon reactive intermediates (silylenes, R2Si) are used to prepare highly strained trans-cycloalkenes. Although strained cycloalkenes show promise for the development of efficient routes for the synthesis of biologically active natural products, the construction of strained cyclic alkenes has been difficult. This project explores the synthesis of highly strained seven- and eight-membered ring trans-alkenes and examines the elevated reactivity of these compounds. Studies of new reactions of these compounds focus on reactions that give products that are difficult to prepare using other methods. Additional efforts will address the detailed reaction mechanisms of new reactions that deviate significantly from expected reactivity.