New Catalytic Reactions for Enhanced Synthetic Efficiency

在这个由化学系化学催化计划资助的项目中，斯坦福大学的巴里特罗斯特教授正在开发合成复杂分子的催化反应。该研究通过关注一个重要但经常被忽视的问题-原子经济性来解决原材料的局限性和需要关注的环境问题，即开发反应，其中尽可能最大限度地减少任何化学计量的副产物，并在理想情况下消除，以便产物是反应物的总和，任何额外的试剂仅需要催化。 该提案探索了发明新的反应性范例。例如，由于特罗斯特教授发明了新的合成方法，制药公司的药物发现项目已经出现。该提案概述了一项广泛的研究，以创建新的反应性范例。将探讨过渡金属催化的两个一般领域，即钯和钌。目标是产生原子经济的方法。涉及钯的计划首次探索了用于C-C键形成的新型基底类型。它侧重于一个意想不到的配体效应和基板选择的影响，特别是使用基板轴承氮杂原子，乍一看，预计会失败。涉及钌的计划探索了催化剂结构的设计，以实现以前不存在的反应性和选择性。它设想了碳氮氧杂环的新方法。它提出了通过容易获得的炔丙基衍生物的简单异构化产生类卡宾，重要的反应中间体，从而避免了几乎普遍使用的危险的重氮化合物。

In this project funded by the Chemical Catalysis program of the Chemistry Division, Professor Barry Trost of Stanford University is developing catalytic reactions for the synthesis of complex molecules. The research is addressing limitations of raw materials and environmental concerns that require attention by focusing on an important but frequently overlooked issue - atom economy, i.e. the development of reactions in which, to the greatest extent possible, any stoichiometric by-products are minimized and, in the ideal case, eliminated so that the product is the sum of the reactants with any additional reagent being required only catalytically. This proposal explores inventing new paradigms of reactivity. For example, drug discovery programs at pharmaceutical companies have emerged as a result of Professor Trost's invention of new synthetic methods. The proposal outlines a broad study to create new paradigms of reactivity. Two general areas of transition metal catalysis will be explored, that of palladium and ruthenium. The goal is the generation of atom economical methods. The program involving palladium explores for the first time novel substrate types for C-C bond formation. It focuses on an unexpected ligand effect and the impact of substrate selection, especially using substrates bearing nitrogen heteroatoms which, at first glance, would be expected to fail. The program involving ruthenium explores the design of the structure of the catalyst to enable reactivity and selectivity which previously did not exist. It envisions novel ways to carbo- and nitrogen and oxygen heterocycles. It proposes the generation of carbenoids, important reactive intermediates, by simple isomerization of readily available propargyl derivatives thereby avoiding the almost universal use of hazardous diazo compounds.