New Approaches for Efficiency in Synthetic Organic Chemistry

有机化学中最具挑战性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审查了实现这一目标的新概念。第一个是合理设计用于形成双核和异核金属络合物的配体作为加成反应的催化剂。第二个区域涉及不对称三亚甲基甲烷(TMM)环加成反应。受体的加成发生在TMM单元的表面，远离金属及其伴随配体的位置，这使得不对称诱导具有极大的挑战性。借助于分子模拟，设计了用于[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烷基化反应。利用配基设计，将尝试在更多取代的烯丙基末端进行反位亲核加成，以及在烯丙基单元的C-2位进行反热力学加成。此外，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Ru催化反应中的不对称诱导，以探索它们在烯烃-烯烃偶联和烯丙基烷基化中的探索。有了这个奖项，有机和高分子化学计划支持斯坦福大学化学系的Barry M.Trost教授的研究计划。特罗斯特教授的计划围绕着通过发明新的催化过程来提高合成效率的主题，这些过程增强了化学、区域、非对映和对映体的选择性。特别关注的是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都有影响，特别是在制药和农化工业方面。

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.