Silane Reagents and Catalysts for Asymmetric Synthesis of Carbinamines

Columbia University, New York NY

Investigators

Abstract

The focus of this research will be to carry out the asymmetric allylation (and crotylation, cinnamylation, etc.), Friedel-Crafts, and cycloaddition reactions of aldimines and ketimines using 5-membered ring silanes prepared from chiral amino alcohols and diamines. Silanes, when constrained in a 5-membered ring by 1,2-diols, aminoalcohols, or diamines possess Lewis acidity sufficient for efficient yet mild, highly enantioselective organic transformations. Mechanistic studies designed to elucidate the origin of the effect, and the mechanism of asymmetric induction will be carried out and the application of the proposed reactions to selected problems in target-oriented synthesis, such as the preparation of the marine natural product lepadiformine, will demonstrate the utility of these reagents. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. James L. Leighton in the Department of Chemistry at Columbia University. Professor Leighton will focus his work on the discovery and development of a new family of silicon-containing reagents and catalysts for asymmetric synthesis. The reagents will be developed within the parameters of several criteria defined to maximize the practicality and utility of the reagents. Thus, they will be readily and inexpensively prepared, they will be isolable and stable to storage, they will be environmentally benign, and their use will require no extraordinary techniques or procedures. The work has potential for important broader impact in the pharmaceutical and fines chemicals industries and the project serves as an excellent setting for the training of undergraduates and graduate students.