Iron-Catalyzed Meerwein Carbooxygenation of Electron-Rich Olefins: Studies with Styrenes, Vinyl Pyrrolidinone, and Vinyl Oxazolidinone

Autor(es)

Scarpa de Souza, Edson Leonardo ^[1] ; Wiethan, Carson ^[1] ; Duarte Correia, Carlos Roque ^[1]

Afiliação do(s) autor(es)

^[1] Univ Estadual Campinas, Inst Chem, Dept Organ Chem, Rua Josue de Castro, BR-13083970 Campinas, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: ACS OMEGA; v. 4, n. 20, p. 18918-18929, NOV 12 2019.
• Citações Web of Science: 0

Resumo

The arylative oxygenation of the electron-rich olefins styrene, a-methylstyrene, vinyl pyrrolidinone, and vinyl oxazolidinone was accomplished using arenediazonium salts and catalytic amounts of FeSO4 in an effective single electron transfer radical process. A broad range of aryldiazonium salts was tolerated using water, methanol, or their combination with acetonitrile to furnish the corresponding carbohydroxylated and carbomethoxylated products (42 examples), including functionalized dihydroisocoumarin and dihydrobenzofuran systems in good to excellent yields (up to 88%). The protocols developed for the Fe(II)catalyzed carbohydroxylation were also compared to Ru(II) and Ir(III) photoredox carbooxygenations of these electron-rich olefins. The Fe(II)catalyzed process proved to be highly competitive compared to the photoredox and the uncatalyzed processes. The proposed mechanism for the Fe(II)-catalyzed reactions involves the synergic combination with an effective Fe+2/Fe+3 redox system and a radical polar crossover mechanism featuring an unprecedented capture of the reactive N-acyliminium in the case of vinyl pyrrolidinone and vinyl oxazolidinone. (AU)

• Processo FAPESP: 18/08627-6 - Reações de acoplamento C-C estereosseletivas catalisadas por níquel: design, avaliação de ligantes e aplicações sintéticas
• Beneficiário: Carson Wanderley Wiethan
• Linha de fomento: Bolsas no Brasil - Pós-Doutorado
• Processo FAPESP: 13/07600-3 - CIBFar - Centro de Inovação em Biodiversidade e Fármacos
• Beneficiário: Glaucius Oliva
• Linha de fomento: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
• Processo FAPESP: 14/25770-6 - Novas fronteiras em reações de acoplamento cruzado mediadas por paládio: associando catálise enantiosseletiva, ativações C-H, novos materiais e reações em fluxo visando alta eficiência e sustentabilidade em processos sintéticos
• Beneficiário: Carlos Roque Duarte Correia
• Linha de fomento: Auxílio à Pesquisa - Temático