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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.)

Olefin Cyclopropanation by Radical Carbene Transfer Reactions Promoted by Cobalt(II)/Porphyrinates: Active-Metal-Template Synthesis of [2]Rotaxanes

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Author(s):
Alcantara, Arthur F. P. [1, 2] ; Fontana, Liniquer A. [1] ; Rigolin, Vitor H. [1] ; Andrade, Yuri F. S. [1] ; Ribeiro, Marcos A. [1] ; Barros, Wdeson P. [1] ; Ornelas, Catia [1] ; Megiatto, Jr., Jackson D. [1]
Total Authors: 8
Affiliation:
[1] Univ Campinas UNICAMP, Inst Chem, POB 6154, BR-13083970 Campinas, SP - Brazil
[2] Inst Fed Sertao Pernambucano, Estr Tamboril, BR-56200000 Ouricuri, PE - Brazil
Total Affiliations: 2
Document type: Journal article
Source: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION; v. 57, n. 29, p. 8979-8983, JUL 16 2018.
Web of Science Citations: 4
Abstract

A Co-II/porphyrinate-based macrocycle in the presence of a 3,5-diphenylpyridine axial ligand functions as an endotopic ligand to direct the assembly of {[}2]rotaxanes from diazo and styrene half-threads, by radical-carbene-transfer reactions, in excellent 95% yield. The method reported herein applies the active-metal-template strategy to include radical-type activation of ligands by the metal-template ion during the organometallic process which ultimately yields the mechanical bond. A careful quantitative analysis of the product distribution afforded from the rotaxane self-assembly reaction shows that the Co-II/porphyrinate subunit is still active after formation of the mechanical bond and, upon coordination of an additional diazo half-thread derivative, promotes a novel intercomponent C-H insertion reaction to yield a new rotaxane-like species. This unexpected intercomponent C-H insertion illustrates the distinct reactivity brought to the Co-II/porphyrinate catalyst by the mechanical bond. (AU)

FAPESP's process: 13/22160-0 - Development of original synthetic strategies for the preparation of supramolecular Interlocked polymers
Grantee:Jackson Dirceu Megiatto Junior
Support type: Research Grants - Young Investigators Grants
FAPESP's process: 15/22379-7 - Multifunctional molecular magnetic systems: synthesis and study of magnetic, luminescent and photorreactive properties of polinuclear complexes containing transition and lanthanide metal ions
Grantee:Wdeson Pereira Barros
Support type: Regular Research Grants
FAPESP's process: 17/06752-5 - Development of New Template Strategies for the Synthesis of Polyrotaxanes
Grantee:Liniquer Andre Fontana
Support type: 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 type: Regular Research Grants