Decarboxylative Hydroalkylation of Alkynes via Dual Copper- Photoredox Catalysis

A photoredox strategy for the synthesis of a wide range of allylic amines and ethers from carboxylic acids and alkynes has been developed. This approach relies on the perturbation of the ground-state electronic properties of terminal alkynes through the formation and photoexcitation of copper acetyl...

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Detalhes bibliográficos
Autores: Mastandrea, Marco M., Cañellas, Santiago, Caldentey, Xisco, Pericàs, Miquel A.
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2020
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositório:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/450564
Acesso em linha:http://hdl.handle.net/2072/450564
https://doi.org/10.1021/acscatal.0c01742
Access Level:Acceso aberto
Palavra-chave:54
Descrição
Resumo:A photoredox strategy for the synthesis of a wide range of allylic amines and ethers from carboxylic acids and alkynes has been developed. This approach relies on the perturbation of the ground-state electronic properties of terminal alkynes through the formation and photoexcitation of copper acetylide intermediates. This process takes place through cooperative copper and organic photoredox catalysis and can be carried out in a stereodivergent manner. Thus, a systematic multivariate HTE screening spotlighted that a switch in the stereochemical outcome can be provoked by choosing an appropriate combination of ligand and base. The developed methodology has been applied to the stereoselective coupling of primary, secondary, and tertiary alkyl radicals with (hetero)aromatic terminal alkynes. As an additional practicality, similar reaction conditions allowed for the use of aromatic amines as radical precursors in a cross dehydrogenative coupling for the direct vinylation of inactivated C–H bonds.