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.

在有机化学中最苛刻的挑战之一是通过催化方法引入手性。 该项目在四个不同的领域研究实现这一目标的新概念。 第一个是合理设计配体，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的三亚甲基甲烷（TMM）环加成。 受体的添加发生在TMM单元的远离金属及其伴随配体所在的表面上的事实使得不对称诱导具有高度挑战性。 借助分子模拟，设计了[3+2]、[3+4]和[3+6]环加成反应的新配体家族。 第三部分考察了钯和钼催化的不对称烯丙基烷基化反应。 使用配体设计，contrasteric亲核加成到更多取代的烯丙基末端以及contrathermodynamic加成到烯丙基单元的C-2位置将被尝试。 新的Ru-Pd顺序反应的不对称合成也将进行研究。 第四个领域是钌催化反应中的不对称诱导，用于探索烯烃-炔偶联和烯丙基烷基化反应。有了这个奖项，有机和大分子化学计划支持巴里M教授的研究计划。斯坦福大学化学系的特罗斯特说。 Trost教授的课程围绕着通过发明新的催化过程来提高合成效率的主题，这些催化过程可以增强化学，区域，非对映体和对映体的选择性。 特别关注提高原子经济性的过程，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的各个领域产生了影响，特别是在制药和农业化学工业方面。