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Title: Palladium-catalysed enolate arylation in the synthesis of aromatic heterocycles and substituted heterocycles
Author: Esteves, Carlos Henrique Alves
ISNI:       0000 0004 6494 5222
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2017
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Chapter 1. Introduction A literature background on the early development of the Pd-catalysed cross-coupling reactions and the later discovery of the enolate arylation reaction is presented. In the second part, the literature on pyruvate chemistry is explored, focusing on enantioselective transformations and the synthesis of α-arylated pyruvate derivatives. The final part presents reported protocols on the synthesis of β-carboline, isoquinoline and indole esters, from the classical approaches to the more recent methodologies based on metal catalysed transformations. Chapter 2. Results and Discussion 2.1 A study towards the synthesis of substituted amino-pyridines via 6π-electrocyclisation of 1-azatrienes is presented. The aspects impacting the efficiency of the cyclisation reaction are discussed using the experimental data collected and kinetic experiments published by other groups. 2.2 A synthetic methodology for the synthesis of substituted β-carbolines from 3-bromoindoles and commercially available ketones via Pd-catalysed enolate arylation is discussed. The α-functionalisation of the keto-indole intermediate with electrophiles provided access to C4-functionalised β-carbolines. The one-pot protocol for this sequence was also developed. 2.3 A protected pyruvate equivalent that allows the α-arylation and α-arylation/alkylation reactions to be carried out at the methyl group via Pd-catalysed enolate arylation is presented. The deprotection of the OBO moiety allows the formation mono and multiply α-functionalised pyruvates. 2.4 The synthesis of isoquinoline, β-carboline and indole esters via Pd-catalysed enolate arylation of the OBO-protected pyruvate equivalent developed in this thesis is demonstrated. The functionalisation of these heterocycles via α-alkylation of the aryl-ketone intermediates is also discussed and some examples synthesised to validate the methodology.
Supervisor: Donohoe, Timothy J. Sponsor: Capes - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior ; Brazil
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available