Selective C—H oxidations for complex molecule synthesis and diversification
type: CreativeWork
description: Synthetic chemists are continually challenged to develop more efficient and selective methods for the synthesis of both simple and complex molecules. Traditionally, starting materials for synthesis are derived from petroleum or other natural sources and have been pre-oxidized and pre-activated with reactive functional groups. These functional groups readily participate in a wide range of C—C and other bond forming processes, oxidations, and reductions, referred to as functional group manipulations. In contrast, the C—H bonds that make up the majority of organic frameworks are generally viewed as an inert scaffold upon which the chemistry of other functional groups takes place. Recently a novel strategy for synthesis has emerged that seeks to eliminate the requirement for pre-oxidation and carry out synthetic manipulations directly from a C—H bond, establishing it not simply as a bystander, but as a functional group in its own right. As a result, feedstock materials may be more rapidly transformed into final products. Nature has recognized the power of this approach and routinely oxidizes C—H bonds directly for the purpose of biosynthesis or metabolism. However, central to the application of C—H oxidation in the laboratory is the ability to not only break C—H bonds, but do so in a selective and predictable way. This work describes the development of novel C—H oxidation processes and strategies for their application to the synthesis and diversification of organic molecules. First, harnessing the abundance and simplicity of α-olefins as starting materials, a Pd(II)/bis-sulfoxide catalyst is utilized to carry out a selective intramolecular allylic C—H oxidation to generate a versatile synthetic intermediate (1,4-dioxanones). In contrast to many C—H oxidations, which transform a simple starting material into a single value added product, dioxanones can diverge to form motifs prevalent in natural products (i.e. differentially protected 1,2-diols, polyoxidized motifs and s…
abstract: Synthetic chemists are continually challenged to develop more efficient and selective methods for the synthesis of both simple and complex molecules. Traditionally, starting materials for synthesis are derived from petroleum or other natural sources and have been pre-oxidized and pre-activated with reactive functional groups. These functional groups readily participate in a wide range of C—C and other bond forming processes, oxidations, and reductions, referred to as functional group manipulations. In contrast, the C—H bonds that make up the majority of organic frameworks are generally viewed as an inert scaffold upon which the chemistry of other functional groups takes place. Recently a novel strategy for synthesis has emerged that seeks to eliminate the requirement for pre-oxidation and carry out synthetic manipulations directly from a C—H bond, establishing it not simply as a bystander, but as a functional group in its own right. As a result, feedstock materials may be more rapidly transformed into final products. Nature has recognized the power of this approach and routinely oxidizes C—H bonds directly for the purpose of biosynthesis or metabolism. However, central to the application of C—H oxidation in the laboratory is the ability to not only break C—H bonds, but do so in a selective and predictable way. This work describes the development of novel C—H oxidation processes and strategies for their application to the synthesis and diversification of organic molecules. First, harnessing the abundance and simplicity of α-olefins as starting materials, a Pd(II)/bis-sulfoxide catalyst is utilized to carry out a selective intramolecular allylic C—H oxidation to generate a versatile synthetic intermediate (1,4-dioxanones). In contrast to many C—H oxidations, which transform a simple starting material into a single value added product, dioxanones can diverge to form motifs prevalent in natural products (i.e. differentially protected 1,2-diols, polyoxidized motifs and s…
author: Gormisky, Paul
language: en
keywords: Organic Chemistry, Organic Synthesis, C-H Oxidation, Catalyst Control, Synthetic Streamlining, Oxidative Heck Vinylation
date published: 2014-05-30T16:51:18Z
date modified: 2026-07-22T22:25:38Z
provider: University of Illinois - Urbana-Champaign
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Illinois at Urbana-Champaign

PropertyValue
property ID: Handle
value: http://hdl.handle.net/2142/49588