Control over the Redox Cooperative Mechanism of Radical Carbene Transfer Reactions for the Efficient Active-Metal-Template Synthesis of [2]Rotaxanes

Autor(es)

Alcantara, Arthur F. P. ^{[1, 2]} ; Fontana, Liniquer A. ^[1] ; Almeida, Marlon P. ^[1] ; Rigolin, Vitor H. ^[1] ; Ribeiro, Marcos A. ^[3] ; Barros, Wdeson P. ^[1] ; Megiatto, Jr., Jackson D. ^[1]

Afiliação do(s) autor(es)

^[1] Univ Campinas UNICAMP, Inst Chem, POB 6154, BR-13083970 Campinas - Brazil

^[2] Inst Fed Sertao Pernambucano, Estrada Tamboril, BR-56200000 Ouricuri - Brazil

^[3] Univ Fed Espirito Santo, Dept Quim, Ave Fernando Ferrari 514, BR-29075910 Vitoria, ES - Brazil

• Tipo de documento: Artigo Científico
• Fonte: CHEMISTRY-A EUROPEAN JOURNAL; v. 26, n. 35, p. 7808-7822, JUN 23 2020.
• Citações Web of Science: 4

Resumo

A 5,15-bis(1,1 `-biphenyl)porphyrin-based molecular clip covalently connected to a ditopic aliphatic ester loop moiety yields a semi-rigid macrocycle with a well-defined cavity. The resulting macrocycle fits the structural requirements for the preparation of porphyrinates capable of promoting formation of C-C bonds. To demonstrate the usefulness of porphyrin-based macrocycles, an active-metal-template synthesis of rotaxanes through a redox non-innocent carbene transfer reaction is described. Coordination of Co-II ions into the porphyrin subunit followed by addition of appropriate monodentate nitrogen-based additives to function as axial ligands enables the radical carbene transfer reactions to styrene derivatives to occur exclusively through the cavity of the macrocycle to afford cyclopropane-linked rotaxanes in excellent 95 % yield. Investigation of the product distribution afforded from the rotaxane assembly reaction reveals how the redox cooperative action between the carbene species and the Co-II ions can be manipulated to gain control over the radical-type mechanism to favor the productive rotaxane forming process. (AU)

• Processo FAPESP: 17/06752-5 - Desenvolvimento de Novas Estratégias Sintéticas para Preparação de Polirotaxanas
• Beneficiário: Liniquer André Fontana
• Modalidade de apoio: Bolsas no Brasil - Doutorado
• Processo FAPESP: 15/23761-2 - Desenvolvimento de novos dendrímeros multifuncionais com estrutura bem definida para aplicações em nanomedicina
• Beneficiário: Cátia Cristina Capêlo Ornelas Megiatto
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 13/22160-0 - Desenvolvimento de estratégias sintéticas originais para preparar polímeros supramoleculares entrelaçados
• Beneficiário: Jackson Dirceu Megiatto Junior
• Modalidade de apoio: Auxílio à Pesquisa - Jovens Pesquisadores