δ-Amination of alkyl alcohols via energy transfer photocatalysis

Amino alcohols play a crucial role in the realm of biologically active compounds due to their functional diversity. In this study, we introduce a metal-free energy transfer photocatalytic method for the preparation of 1,4-aminoalcohols from readily available alcohol feedstocks. The key feature of th...

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Detalhes bibliográficos
Autores: Cristóbal Gordo, Christian, Alonso Montero, María Inés, Tato, Francisco, Cabrera Afonso, María Jesús, Adrio Sevilla, Francisco Javier, Ribagorda Lobera, María
Formato: artículo
Fecha de publicación:2024
País:España
Recursos:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/716920
Acesso em linha:http://hdl.handle.net/10486/716920
https://dx.doi.org/10.1039/D4QO01522C
Access Level:acceso abierto
Palavra-chave:Amination
Amines
Carboxylation
Photocatalytic Activity
Química
Descrição
Resumo:Amino alcohols play a crucial role in the realm of biologically active compounds due to their functional diversity. In this study, we introduce a metal-free energy transfer photocatalytic method for the preparation of 1,4-aminoalcohols from readily available alcohol feedstocks. The key feature of this transformation is the simultaneous generation of a persistent iminyl radical and a transient carbon-centered radical through σ-homolytic cleavage of the O–N bond via energy transfer (EnT). The process involves fragmentation/decarboxylation/1,5-HAT (hydrogen atom transfer), leading to the formation of a C(sp3)-hybridized radical, which undergoes selective radical–radical cross-coupling or a radical chain event to yield the desired products. In addition, the protocol was also found to be suitable for N-tosyl amines, giving rise to 1,4-diamines. Our approach combines experimental mechanistic investigations with detailed computational studies using density functional theory (DFT) to provide insights into the reaction mechanism. This innovative method provides a new approach for preparing δ-amino alkyl alcohols and amines