New Approaches for Efficiency in Synthetic Organic Chemistry

有机化学中最艰巨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探讨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甲基乙烷（TMM）环加成。事实上，受体的添加发生在金属及其伴随的配体驻留的远端TMM单元的表面，这使得不对称诱导极具挑战性。在分子模拟的帮助下，为[3+2]、[3+4]和[3+6]环加成设计了新的配体家族。第三部分考察了钯和钼催化的不对称烯丙基烷基化。利用配体设计，对比亲核加成到取代较多的烯丙基末端，以及对比热力学加成到烯丙基单元的C-2位置。还将研究用于不对称合成的新型Ru-Pd序列反应。四是Ru催化反应的不对称诱导，探索烯烃-炔偶联和烯丙基烷基化反应。通过这个奖项，有机和大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。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、区域、非映对和对映对映选择性。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。成功的影响范围从材料科学到生物学，特别是在制药和农业工业方面。

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.