Oxidative Heck Reactions with Terminal Olefins
type: CreativeWork
description: Sequential transformations in a single reaction have the potential to dramatically increase efficiency with respect to resources, time, and number of steps to access key intermediates. When sequential C-H bonds are activated a bifunctional handle arises from seemingly inert functionality. This work describes a one-pot sequential allylic C-H esterification, vinylic C-H arylation. A previously reported Pd(II)/sulfoxide system is used to generate branched allylic esters from α-olefins with only the addition of an aryl boronic acid to the reaction mixture. Styrenyl allylic esters are generated in good overall yield and excellent selectivities. The wide functional group tolerance and mild conditions of this three-component coupling reaction provide an attractive manifold for the rapid build-up of dense functionality around terminal olefins with minimal protecting group strategies or undesirable oxidation/reduction reactions.The synthetic utility of this reaction has been demonstrated through the synthesis of several intermediates to biologically active molecules. The ready availability and inertness of α-olefins relative to the oxidized precursors required for other C—C bond forming methods means that fewer steps are required for their installation and maintenance throughout a synthetic sequence. Previously, allylic esters served as non-resonance directing groups on terminal olefin for the vinylic C—H arylation (Heck reaction). This manifold is unique because previous intermolecular Heck reaction conditions require an excess of resonance activated olefin coupling partner. Further exploration of directing groups to determine the underlying directing factors led to the discovery of several terminal olefin classes with diversedirecting elements. A general and highly selective intermolecular Heck arylation of non-resonance stabilized α-olefins with aryl and stryenyl boronic reagents has been developed. The Pd(II)/sulfoxide catalyzed Heck reaction is performed under oxidative…
abstract: Sequential transformations in a single reaction have the potential to dramatically increase efficiency with respect to resources, time, and number of steps to access key intermediates. When sequential C-H bonds are activated a bifunctional handle arises from seemingly inert functionality. This work describes a one-pot sequential allylic C-H esterification, vinylic C-H arylation. A previously reported Pd(II)/sulfoxide system is used to generate branched allylic esters from α-olefins with only the addition of an aryl boronic acid to the reaction mixture. Styrenyl allylic esters are generated in good overall yield and excellent selectivities. The wide functional group tolerance and mild conditions of this three-component coupling reaction provide an attractive manifold for the rapid build-up of dense functionality around terminal olefins with minimal protecting group strategies or undesirable oxidation/reduction reactions.The synthetic utility of this reaction has been demonstrated through the synthesis of several intermediates to biologically active molecules. The ready availability and inertness of α-olefins relative to the oxidized precursors required for other C—C bond forming methods means that fewer steps are required for their installation and maintenance throughout a synthetic sequence. Previously, allylic esters served as non-resonance directing groups on terminal olefin for the vinylic C—H arylation (Heck reaction). This manifold is unique because previous intermolecular Heck reaction conditions require an excess of resonance activated olefin coupling partner. Further exploration of directing groups to determine the underlying directing factors led to the discovery of several terminal olefin classes with diversedirecting elements. A general and highly selective intermolecular Heck arylation of non-resonance stabilized α-olefins with aryl and stryenyl boronic reagents has been developed. The Pd(II)/sulfoxide catalyzed Heck reaction is performed under oxidative…
author: Delcamp, Jared H.
language: en
keywords: Heck reaction, oxidative, Palladium, arylation, vinylation, transition metal catalysis
date published: 2011-01-21T22:52:16Z
date modified: 2026-07-22T22:25:11Z
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/2142/18626