New Catalytic Reactions for Enhanced Synthetic Efficiency

提高合成效率的新催化反应

• 批准号: 1360634
• 负责人: Barry Trost
• 金额: $ 88万
• 依托单位: Stanford University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-06-15 至 2018-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1360634&HistoricalAwards=false
• 关键词: New; Catalytic; Reactions; Enhanced; Synthetic

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.

在这个由化学部化学催化项目资助的项目中，斯坦福大学的巴里·特罗斯特教授正在开发用于合成复杂分子的催化反应。该研究正在解决需要关注的原材料限制和环境问题，重点关注一个重要但经常被忽视的问题——原子经济，即反应的发展，其中尽可能减少任何化学计量副产物，并且，在理想情况下，消除，以便产物是反应物与仅需要催化作用的任何附加试剂的总和。 该提案探讨了发明新的反应范式。例如，由于 Trost 教授发明了新的合成方法，制药公司的药物发现项目应运而生。该提案概述了一项广泛的研究，以创建新的反应范式。将探索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方法。涉及钯的项目首次探索了用于 C-C 键形成的新型底物类型。它重点关注意想不到的配体效应和底物选择的影响，特别是使用带有氮杂原子的底物，乍一看，预计会失败。该项目涉及钌，探索催化剂结构的设计，以实现以前不存在的反应性和选择性。它设想了碳杂环、氮杂环和氧杂环的新方法。它提出通过容易获得的炔丙基衍生物的简单异构化来生成类胡萝卜素（重要的反应中间体），从而避免几乎普遍使用危险的重氮化合物。