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General and Anti-Markovnikov Selective Ni-Catalyzed Alkylation of Arenes and Heteroarenes with Non-Activated Olefins

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Autor(es):
Scarpa de Souza, Edson Leonardo ; Ahrens, Sebastian ; Junge, Kathrin ; Quesada, Jorge ; Beller, Matthias
Número total de Autores: 5
Tipo de documento: Artigo Científico
Fonte: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY; v. N/A, p. 5-pg., 2025-08-06.
Resumo

The majority of C-C coupling reactions between arenes and olefins result in the formation of branched isomer products, exhibiting what is known as Markovnikov selectivity. However, alternative catalytic strategies are required to modulate this selectivity, thereby yielding linear isomer products that are crucial for various significant applications. In this study, a straightforward Ni-0-N-heterocyclic carbene (NHC) catalyst is presented for the anti-Markovnikov hydroarylation of unactivated olefins with arenes (benzene) and heteroarenes (pyridine, indole, and imidazopyridine derivatives). The active catalyst species are in situ generated from NHC ligands and a stable Ni-II salt that is reduced by an alkaline hydride (NaH, LiH). This strategy circumvents the elaborate procedures that have been employed to synthesize and isolate Ni-0-NHC complexes. The assessment of >15 reactions between olefins and (hetero)arenes shows the formation of linear isomers as the predominant products, with yields ranging from moderate to excellent and exceptional selectivity. (AU)

Processo FAPESP: 22/14575-4 - Síntese enantiosseletiva de esqueletos 2,3-difenilpropanoato via reações de Heck-Matsuda carbonilativas
Beneficiário:Edson Leonardo Scarpa de Souza
Modalidade de apoio: Bolsas no Exterior - Estágio de Pesquisa - Doutorado
Processo FAPESP: 19/25657-9 - Arilações radicalares de enecarbamatos endocíclicos via fotoredox: desenvolvimento do novo método, derivatizações e aplicações sintéticas
Beneficiário:Edson Leonardo Scarpa de Souza
Modalidade de apoio: Bolsas no Brasil - Doutorado