Aerobic Oxidations of Alcohols in Organic Synthesis

University Of Utah, Salt Lake City UT

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Abstract

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.