Aerobic Oxidations of Alcohols in Organic Synthesis

描述：(申请人提供)将醇氧化成醛和 酮类化合物是有机合成中普遍存在的官能团转化。 在此描述的项目的总体目标是开发实用的 以分子氧为基团的反应的氧化和催化剂 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， 以及对环境无害的副产品水和/或氢的形成 过氧化氢。好氧醇氧化金属催化剂的研究进展 将专注于对映体选择性氧化。具体的例子有 仲丙醇氧化动力学拆分的对映体选择性催化剂 醇和介孔二醇的氧化去对称化。两种反应 为有机合成提供潜在的手性构件。一个新的 甲醇好氧氧化对映体选择性催化剂的研制 这个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。这个 将使用一种新发现的金属介导的还原剂来制备二胺 通过环合复分解将亚胺与进一步的精制偶联。这个 对映选择性好氧氧化的机理将是同时存在的 考察了哪些实验用于阐明对映体的测定 并提出了确定速率的步骤。一种开发A/S的方法 概述了常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.