Hidro- & deuterocarbamoilação do alceno de Karady-Beckwith: síntese estereosseletiva da asparagina e seus derivados N4-substituídos

• Ano de defesa: 2023
• Autor(a) principal: Moro, Pedro Augusto Marocco
• Orientador(a): Paixão, Márcio Weber
• Tipo de documento: Dissertação
• Tipo de acesso: Acesso aberto
• Idioma: por
• Instituição de defesa: Universidade Federal de São Carlos; Câmpus São Carlos
• Programa de Pós-Graduação: Programa de Pós-Graduação em Química - PPGQ
• Palavras-chave em Português: Aminoácidos não-naturais; Organofotocatálise; Alceno de Karady-Beckwith; Dehidroalanina; Radicais carbamoil; Fluxo-contínuo
• Palavras-chave em Inglês: Non-natural amino acids; Organophotocatalysis; Karady-Beckwith alkene; Dehydroalanine; Carbamoyl radicals; Continuous flow
• Área do conhecimento CNPq: CIENCIAS EXATAS E DA TERRA::QUIMICA; CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::FOTOQUIMICA ORGANICA; CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA
• Link de acesso: https://repositorio.ufscar.br/handle/20.500.14289/18951

The development of sustainable stereoselective methodologies for obtaining compounds of synthetic and biological relevance is highly important in contemporary times. In this regard, the synthesis of non-natural amino acids appears as a possible tool for modulating the properties of small molecules, peptides, and proteins. Visible light has been gaining increasing prominence among the methodologies used for obtaining amino acid derivatives. The use of light presents a good alternative due to its generally mild reaction conditions compared to classical thermal methodologies. Our research group has been developing photocatalytic methodologies for the synthesis of small molecules as well as amino acids and peptide modification. The present work explored the stereoselective synthesis of non-natural amino acids derived from Asparagine. Karady-Beckwith alkene was used as a radical acceptor, 4-carbamoyl dihydropyridines as a source of carbamoyl radicals, and the organophotocatalyst 4CzIPN for the preparation of 23 hydro- and deuterocarbamoylated derivatives in batch and continuous flow. The methodology allowed for the stereoselective synthesis of amino acid derivatives with good to excellent yields under mild conditions and metal-free.