Development of efficient chemoselective TEMPO oxidations of alcohols under continuous flow conditions and using a supported catalyst

在连续流动条件下并使用负载型催化剂开发高效的醇化学选择性 TEMPO 氧化反应

• 批准号: 538043-2018
• 负责人: Charette, André
• 金额: $ 1.82万
• 依托单位: Université de Montréal
• 依托单位国家: 加拿大
• 项目类别: Engage Grants Program
• 财政年份: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=647215
• 关键词: Development; efficient; chemoselective; TEMPO; oxidations

The oxidation reaction of alcohols is one of the most fundamental and widely used transformation in organic**chemistry. Traditionally, these oxidations have been carried out in batch (and even on process scale) using**stoichiometric amount of highly toxic metals or stoichiometric harmful reagents. A few years ago, several**methods relying on the use of catalytic tetramethylpiperidine N-Oxide (TEMPO) completely changed the way**these oxidations were carried out. In combination with a stoichiometric oxidant (typically bleach), alcohols can**be converted to aldehydes and/or carboxylic acids or esters. One drawback of this catalyst is its cost. One**potential solution to this problem is to use a supported version of TEMPO that could be recycled. This**proposal, implying a strong collaboration between the industrial partner and the UdeM's group aims at**synthesizing new TEMPO-supported resins catalysts for applications in oxidation chemistry under continuous**flow conditions. New resins with various pore sizes, loading, and particule sizes will be synthesized and tested**in oxidation chemistry. Other selective TEMPO oxidation procedures that are compatible with a continuous**flow process will be developed to ensure that cheap and readily available oxidants can be used. Continuous**flow synthesis (or micro-reactor technology) has emerged as a unique technique that allows making chemical**transformations more efficiently, more selectively, and with higher degrees of safety.**The goal will be to develop conditions that are specific to primary vs secondary alcohols as well as preventing**or inducing over oxidation. It is expected that this new tools should be widely used by the scientific**community.

醇的氧化反应是有机**化学中最基本和广泛使用的转化之一。传统上，这些氧化是使用**化学计量量的高毒金属或化学计量有害试剂分批进行的（甚至是过程尺度）。几年前，依赖于使用催化四甲基哌啶N-氧化物（TEMPO）的几种**方法完全改变了这些氧化的方式。结合化学计量氧化剂（通常是漂白剂），醇可以**转化为醛和/或羧酸或酯。该催化剂的一个缺点是其成本。解决此问题的一种潜在解决方案是使用可以回收的速度的支持版本。这项**建议意味着工业合作伙伴与UDEM小组之间的强烈合作旨在**综合新的节气支持的树脂催化剂，以在连续**流动条件下用于氧化化学中的应用。在氧化化学中，将合成和测试具有各种孔径，负载和颗粒大小的新树脂。将开发与连续**流程兼容的其他选择性节奏氧化程序，以确保可以使用便宜且易于使用的氧化剂。连续的**流量合成（或微反应技术）已成为一种独特的技术，它允许更有效，更有选择地使化学**变换更有效，并且具有更高的安全性。预计该新工具应由科学**社区广泛使用。