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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

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

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Author(s):
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]
Total Authors: 7
Affiliation:
[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
Total Affiliations: 3
Document type: Journal article
Source: CHEMISTRY-A EUROPEAN JOURNAL; v. 26, n. 35, p. 7808-7822, JUN 23 2020.
Web of Science Citations: 4
Abstract

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)

FAPESP's process: 17/06752-5 - Development of New Template Strategies for the Synthesis of Polyrotaxanes
Grantee:Liniquer André Fontana
Support Opportunities: Scholarships in Brazil - Doctorate
FAPESP's process: 15/23761-2 - Development of new well-defined multifunctional dendrimers for applications in nanomedicine
Grantee:Cátia Cristina Capêlo Ornelas Megiatto
Support Opportunities: Regular Research Grants
FAPESP's process: 13/22160-0 - Development of original synthetic strategies for the preparation of supramolecular Interlocked polymers
Grantee:Jackson Dirceu Megiatto Junior
Support Opportunities: Research Grants - Young Investigators Grants