4.6 Article

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

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 26, Issue 35, Pages 7808-7822

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201905602

Keywords

carbenes; cyclopropanation; porphyrinoids; radical chemistry; rotaxanes

Funding

  1. FundacAo de Amparo a Pesquisa do Estado de SAo Paulo (FAPESP) [2013/22160-0, 2015/23761-2, 2017/06752-5]
  2. Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) [301899/2014-2]
  3. CoordenacAo de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)

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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.

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