New Approaches for Efficiency in Synthetic Organic Chemistry

提高有机合成化学效率的新方法

• 批准号: 0846427
• 负责人: Barry Trost
• 金额: $ 94.25万
• 依托单位: Stanford University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-02-01 至 2012-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0846427&HistoricalAwards=false
• 关键词: New; Approaches; Efficiency; Synthetic; Organic

Among the most demanding challenges in organic chemistry is the introduction of chirality via catalytic methods. This project examines new concepts towards this goal in four disparate areas. The first involves the rational design of ligands for formation of dinuclear and heterodinuclear metal complexes as catalysts for addition reactions. The second area involves asymmetric trimethylenemethane (TMM) cycloadditions. The fact that the addition of the acceptor occurs on the face of the TMM unit distal to where the metal and its attendant ligands reside makes asymmetric induction highly challenging. With the aid of molecular modeling, new ligand families have been designed for [3+2], [3+4], and [3+6] cycloadditions. The third section examines Pd and Mo catalyzed asymmetric allylic alkylation. Using ligand design, contrasteric nucleophilic addition to the more substituted allyl terminus as well as contrathermodynamic addition to the C-2 position of the allyl unit will be attempted. Novel Ru-Pd sequential reactions for asymmetric synthesis will also be studied. The fourth area is the asymmetric induction in Ru catalyzed reactions for their exploration in alkene-alkyne coupling and allylic alkylations.With this award, the Organic and Macromolecular Chemistry Program supports the research program of Professor Barry M. Trost of the Department of Chemistry at Stanford University. Professor Trost's program revolves around the theme of enhancing synthetic efficiency by inventing new catalytic processes that exercise enhanced chemo-, regio-, diastereo-, and enantio-selectivity. Particular attention focuses on processes that enhance atom economy, a key aspect of "green chemistry". Success has impacts on areas ranging from materials science to biology, especially with respect to the pharmaceutical and agrichemical industries.

有机化学中最严峻的挑战之一是通过催化方法引入手性。 该项目在四个不同领域研究了实现这一目标的新概念。 第一个涉及合理设计配体，以形成双核和异双核金属配合物作为加成反应的催化剂。 第二个领域涉及不对称三亚甲基甲烷（TMM）环加成。 事实上，受体的添加发生在远离金属及其伴随配体所在位置的 TMM 单元表面，这使得不对称感应极具挑战性。 在分子建模的帮助下，新的配体家族被设计用于[3+2]、[3+4]和[3+6]环加成。 第三部分研究了 Pd 和 Mo 催化的不对称烯丙基烷基化。 使用配体设计，将尝试对更多取代的烯丙基末端进行对比亲核加成，以及对烯丙基单元的C-2位置进行逆热力学加成。 还将研究用于不对称合成的新型 Ru-Pd 顺序反应。 第四个领域是钌催化反应中的不对称诱导，以探索烯烃-炔烃偶联和烯丙基烷基化反应。有机与高分子化学项目支持斯坦福大学化学系 Barry M. Trost 教授的研究项目。大学。 Trost 教授的项目围绕着通过发明新的催化过程来提高合成效率的主题，这些过程可以增强化学选择性、区域选择性、非对映选择性和对映选择性。 特别关注增强原子经济性的过程，这是“绿色化学”的一个关键方面。 成功对从材料科学到生物学等领域都有影响，特别是在制药和农化行业。