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化学中最基本、最广泛应用的转化反应之一。传统上，这些氧化是使用**化学计量的剧毒金属或化学计量的有害试剂批量（甚至在工艺规模）进行的。几年前，几种依赖于使用催化四甲基哌啶 N-氧化物 (TEMPO) 的方法完全改变了这些氧化的进行方式。与化学计量氧化剂（通常是漂白剂）结合，醇可以转化为醛和/或羧酸或酯。这种催化剂的一个缺点是其成本。此问题的一个潜在解决方案是使用可回收的受支持版本的 TEMPO。该**提案意味着工业合作伙伴与 UdeM 团队之间的强有力合作，旨在**合成新型 TEMPO 支撑的树脂催化剂，用于连续**流动条件下的氧化化学应用。具有不同孔径、负载量和颗粒尺寸的新树脂将在氧化化学中合成和测试**。将开发与连续**流程兼容的其他选择性 TEMPO 氧化程序，以确保可以使用廉价且易于获得的氧化剂。连续**流合成（或微反应器技术）已成为一种独特的技术，可以使化学**转化更有效、更具选择性且安全性更高。**目标是开发特定的条件伯醇与仲醇的比较以及防止**或诱导过度氧化。预计这种新工具应该被科学界广泛使用。