Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 29, Pages 8979-8983Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201803934
Keywords
porphyrinoids; carbenes; radicals; rotaxanes; supramolecular chemistry
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Funding
- Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2013/22160-0, 2015/22379-7, 2015/23761-2, 2017/06752-5]
- Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) [301899/2014-2, 302453/2014-8]
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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.
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