Palladium-Catalyzed Ortho C-H Arylation of Unprotected Anilines

Metal-catalyzed C-H functionalizations on the aryl ring of anilines usually need cumbersome N-protection-deprotection strategies to ensure chemoselectivity. We describe here the Pd-catalyzed direct C-H arylation of unprotected anilines with no competition of the N-arylation product. The ligand [2,2&...

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Detalhes bibliográficos
Autores: Pinilla, Cintya|||0000-0001-7091-6442, Salamanca, Vanesa|||0000-0001-6470-3934, Lledós, Agustí|||0000-0001-7909-422X, Albéniz, Ana C.|||0000-0002-4134-1333
Tipo de documento: artigo
Data de publicação:2022
País:España
Recursos:Universitat Autònoma de Barcelona
Repositório:Dipòsit Digital de Documents de la UAB
Idioma:inglês
OAI Identifier:oai:ddd.uab.cat:283550
Acesso em linha:https://ddd.uab.cat/record/283550
https://dx.doi.org/urn:doi:10.1021/acscatal.2c05206
Access Level:Acceso aberto
Palavra-chave:C-H activation
Unprotected anilines
Direct arylation
Palladium
Metal-ligand cooperation
Pyridones
Descrição
Resumo:Metal-catalyzed C-H functionalizations on the aryl ring of anilines usually need cumbersome N-protection-deprotection strategies to ensure chemoselectivity. We describe here the Pd-catalyzed direct C-H arylation of unprotected anilines with no competition of the N-arylation product. The ligand [2,2'-bipyridin]-6(1 H)-one drives the chemoselectivity by kinetic differentiation in the product-forming step, while playing a cooperating role in the C-H cleavage step. The latter is favored in an anionic intermediate where the NH moiety is deprotonated, driving the regioselectivity of the reaction toward ortho substitution.