New Catalytic Reactions for Enhanced Synthetic Efficiency

在这个由化学部化学催化项目资助的项目中，斯坦福大学的Barry Trost教授正在开发合成复杂分子的催化反应。这项研究通过关注一个重要但经常被忽视的问题——原子经济——来解决原材料的限制和需要注意的环境问题，即在最大程度上尽可能减少任何化学计量副产物的反应，在理想情况下，消除反应，以便产品是反应物的总和，任何额外的试剂只需要催化。本提案探索发明新的反应性范例。例如，制药公司的药物发现项目是由于特罗斯特教授发明了新的合成方法而出现的。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。目标是生成原子经济方法。涉及钯的项目首次探索了C-C键形成的新型衬底类型。它侧重于意想不到的配体效应和底物选择的影响，特别是使用含有氮杂原子的底物，乍一看，这是预计会失败的。涉及钌的程序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、氮和氧杂环的新方法。它提出了生成类碳化合物，重要的反应中间体，通过简单异构化容易获得的丙炔衍生物，从而避免了几乎普遍使用有害的重氮化合物。

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.