Aerobic Oxidations of Alcohols in Organic Synthesis

描述：（由申请人提供）醇氧化为醛， 酮是有机合成中普遍存在的官能团转化。 本文所述项目的总体目标是开发实用的 氧化和使用分子氧作为催化剂的反应 终端氧化剂分子氧的使用是理想的，部分原因是有利的 使用O2的经济性，O2在普通有机溶剂中的优异溶解性， 以及形成对环境无害的副产物，水和/或氢 过氧化物金属催化剂在醇有氧氧化反应中的研究进展 将专注于对映选择性氧化。具体实例是 用于氧化动力学拆分仲胺的对映选择性催化剂 醇和内消旋二醇的氧化去对称化。两个反应 为有机合成提供了潜在的手性结构单元。一个新 开发的对映选择性催化剂用于醇的有氧氧化， 该实验室为拟议的工作提供了基础。 提出了基于环状1，2-二胺的第二代催化剂。的 二胺将使用新发现的金属介导的还原剂制备， 通过闭环复分解进一步加工亚胺的偶联。的 对映选择性好氧氧化的机理将同时 研究了其中用于阐明对映体决定的实验 和速率确定步骤。制定一个可持续发展战略的方法 概述了室温好氧醇氧化催化剂。

DESCRIPTION: (provided by applicant) The oxidation of alcohols to aldehydes and ketones is a ubiquitous functional group transformation in organic synthesis. The overall goal of the project described herein is to develop practical oxidations and catalysts for reactions that employ molecular oxygen as the terminal oxidant. The use of molecular oxygen is ideal in part due to favorable economics of using O2, excellent solubility of O2 in common organic solvents, and the formation of environmentally benign byproducts, water and/or hydrogen peroxide. The development of metal-catalysts for aerobic alcohol oxidations will focus on enantioselective oxidations. Specific examples are enantioselective catalysts for the oxidative kinetic resolution of secondary alcohols and the oxidative desymmetrization of meso-diols. Both reactions provide potential chiral building blocks for organic synthesis. A newly developed enantioselective catalyst for the aerobic oxidation of alcohols from this laboratory provides the foundation for the proposed work. Second-generation catalysts based on cyclic 1,2-diamines are proposed. The diamines will be prepared using a newly discovered metal-mediated reductive coupling of imines with further elaboration via a ring-closing metathesis. The mechanism of the enantioselective aerobic oxidations will be concurrently investigated in which experiments for the elucidation of the enantiodetermining and rate determining step are proposed. Approaches for the development of a room-temperature aerobic alcohol oxidation catalyst are outlined.