Palladium-Catalysed Functionalisation of Csp3–H Bonds Directed by Aliphatic Amines
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Authors
Buettner, Cornelia
Advisors
Gaunt, Matthew J
Date
2020-08-21Awarding Institution
University of Cambridge
Author Affiliation
Department of Chemistry
Lucy Cavendish
Qualification
Doctor of Philosophy (PhD)
Type
Thesis
Metadata
Show full item recordCitation
Buettner, C. (2020). Palladium-Catalysed Functionalisation of Csp3–H Bonds Directed by Aliphatic Amines (Doctoral thesis). https://doi.org/10.17863/CAM.62230
Abstract
Synthetic transformations on medicinally-relevant aliphatic amines are valuable in the diversification of molecules designed as pharmaceutical agents. This thesis describes two Csp3–H functionalisation reactions, using native amines (secondary and tertiary) to direct C–H activation. Chapter 2 describes a palladium-catalysed Csp3–H acetoxylation directed by native secondary amines. A range of cyclic amines could be acetoxylated with excellent functional group tolerance to form the desired functionalised products. Kinetic experiments and DFT calculations elucidated the mechanism of the transformation, which features C–O bond formation via an external acetate attack onto the electrophilic C–Pd bond. Chapter 3 describes a palladium-catalysed Csp3–H alkenylation directed by tertiary aliphatic amines. A diverse set of amines were functionalised using alkenyl boronic ester coupling partners to give the desired olefinated products. The work includes enantioselective functionalisation using a chiral ligand and a preliminary study of stoichiometric aminoalkyl palladium(II) complexes.
Keywords
C-H Activation, Palladium catalysis
Sponsorship
AstraZeneca
Embargo Lift Date
2022-01-01
Identifiers
This record's DOI: https://doi.org/10.17863/CAM.62230
Rights
All rights reserved
Licence:
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