New Catalytic Asymmetric Methods to Control Axial Chirality in Allenes

得克萨斯大学圣安东尼奥分校化学催化项目授予这一奖项后，圣安东尼奥分校的Frantz教授正在开发新的化学反应，以满足尚未得到满足的合成需求，这些需求广泛地影响了制药、农产品和先进材料等领域小分子的高效制造。作为这一拟议研究计划的一部分，Frantz教授开发了极好的机会，培训各级学生在不对称催化和有机合成方面开发现代方法。在这项研究的发展过程中获得的技术和知识将提高学生在工业和学术职业中的竞争优势。此外，少数族裔和群体、拉美裔和妇女的招募和参与是得到支持的项目的一个关键组成部分。该项目的重点是发现和开发新的催化方法，以从可持续的原料中合成手性联烯。在拟议的资助期内，正在评估各种基于金属的催化剂与手性磷基配体相结合的能力，以促进从中间体阳离子乙烯基钯(II)络合物中消除对映体选择性的β-氢化物，从而有效地控制联烯的轴向手性。具体的探索集中在探索这种新化学的几个转变上，包括乙烯基硼的串联转金属/β-氢化物消除和分子内串联碳金属/β-氢化物的消除。这些转化的一个关键特征是利用了在大多数金属催化过程中通常被视为无效副反应(β-氢化物消除)的反应流形，从而在不对称催化和合成中开辟了一条新的有效途径。

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.