Novel catalytic hydrosilane mediated reduction reactions

This thesis starts with an introduction to the relevant organosilicon and reduction chemistry concepts that underpin the chemistry that is explored in later chapters. In particular, hyperconjugation, relevant organosilicon reagent classes and reduction of carbonyl containing compounds are explored....

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Main Author: Stoll, Emma
Format: Thesis (University of Nottingham only)
Language:English
Published: 2021
Subjects:
Online Access:https://eprints.nottingham.ac.uk/64543/
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author Stoll, Emma
author_facet Stoll, Emma
author_sort Stoll, Emma
building Nottingham Research Data Repository
collection Online Access
description This thesis starts with an introduction to the relevant organosilicon and reduction chemistry concepts that underpin the chemistry that is explored in later chapters. In particular, hyperconjugation, relevant organosilicon reagent classes and reduction of carbonyl containing compounds are explored. Chapter one describes a reductive amination reaction with carboxylic acids in lieu of lower oxidation state alternatives such as aldehydes or alkyl halides. A two-step reaction process is described, whereby the dual reactivity of phenylsilane is exploited in an initial amidation followed by a zinc acetate-catalysed amide reduction. The reaction is applicable to a wide range of substrates and several potential applications have been explored, as well as mechanistic studies. Chapter two builds on the utility of the novel zinc acetate / phenylsilane reduction system for the reduction of carboxylic acids to the corresponding alcohols. However, this time employing the use of zinc acetate and N-methyl morpholine in a dual catalytic system. The protocol is applicable to a wide range of substrates and proceeds via activation using hydrosilanes. Mechanistic studies have also been undertaken to gain insights into the reaction mechanism.
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format Thesis (University of Nottingham only)
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institution University of Nottingham Malaysia Campus
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spelling nottingham-645432025-02-28T15:11:15Z https://eprints.nottingham.ac.uk/64543/ Novel catalytic hydrosilane mediated reduction reactions Stoll, Emma This thesis starts with an introduction to the relevant organosilicon and reduction chemistry concepts that underpin the chemistry that is explored in later chapters. In particular, hyperconjugation, relevant organosilicon reagent classes and reduction of carbonyl containing compounds are explored. Chapter one describes a reductive amination reaction with carboxylic acids in lieu of lower oxidation state alternatives such as aldehydes or alkyl halides. A two-step reaction process is described, whereby the dual reactivity of phenylsilane is exploited in an initial amidation followed by a zinc acetate-catalysed amide reduction. The reaction is applicable to a wide range of substrates and several potential applications have been explored, as well as mechanistic studies. Chapter two builds on the utility of the novel zinc acetate / phenylsilane reduction system for the reduction of carboxylic acids to the corresponding alcohols. However, this time employing the use of zinc acetate and N-methyl morpholine in a dual catalytic system. The protocol is applicable to a wide range of substrates and proceeds via activation using hydrosilanes. Mechanistic studies have also been undertaken to gain insights into the reaction mechanism. 2021-07-31 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en cc_by https://eprints.nottingham.ac.uk/64543/1/Corrected%20Thesis.pdf Stoll, Emma (2021) Novel catalytic hydrosilane mediated reduction reactions. PhD thesis, University of Nottingham. Novel catalytic hydrosilane
spellingShingle Novel catalytic hydrosilane
Stoll, Emma
Novel catalytic hydrosilane mediated reduction reactions
title Novel catalytic hydrosilane mediated reduction reactions
title_full Novel catalytic hydrosilane mediated reduction reactions
title_fullStr Novel catalytic hydrosilane mediated reduction reactions
title_full_unstemmed Novel catalytic hydrosilane mediated reduction reactions
title_short Novel catalytic hydrosilane mediated reduction reactions
title_sort novel catalytic hydrosilane mediated reduction reactions
topic Novel catalytic hydrosilane
url https://eprints.nottingham.ac.uk/64543/