New Catalytic Asymmetric Methods to Control Axial Chirality in Allenes

University Of Texas At San Antonio, San Antonio TX

Investigators

Abstract

With this Award from the Chemical Catalysis Program in the Division of Chemistry, Professor Frantz at the University of Texas at San Antonio is developing new chemical reactions to meet unmet synthetic needs that broadly impact the efficient manufacture of small molecules in areas such as pharmaceuticals, agricultural products, and advanced materials. As a part of this proposed research program, Professor Frantz has developed excellent opportunities to train students at all levels in the development of modern methodologies in asymmetric catalysis and organic synthesis. The techniques and knowledge gained during the development of this research will improve students' competitive edge in both industrial and academic careers. In addition, recruitment and participation by underrepresented minorities and groups, Hispanics and women, is a key component of the supported project. This project focuses on the discovery and development of new catalytic methods to synthesize chiral allenes from sustainable raw materials. In the proposed funding period, various metal-based catalysts in combination with chiral phosphorous-based ligands are being evaluated for their ability to promote an enantioselective beta-hydride elimination from intermediate cationic vinyl Pd(II)-complexes to efficiently control the axial chirality in allenes. Specific explorations focus on several transformations to explore this new chemistry including tandem transmetalation/beta-hydride elimination of vinyl boranes and intramolecular tandem carbometallations/beta-hydride eliminations of alkynes. A key feature of these transformations is the exploitation of a reaction manifold that is typically viewed as an unproductive side-reaction (beta-hydride eliminations) in most metal-catalyzed processes to a new productive avenue in asymmetric catalysis and synthesis.