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Stereoselective Postassembly CH Oxidation of Self-Assembled Metal-Ligand Cage Complexes.
Holloway, Lauren R; Bogie, Paul M; Lyon, Yana; Julian, Ryan R; Hooley, Richard J.
Afiliación
  • Holloway LR; Department of Chemistry, University of California-Riverside , Riverside, California 92521, United States.
  • Bogie PM; Department of Chemistry, University of California-Riverside , Riverside, California 92521, United States.
  • Lyon Y; Department of Chemistry, University of California-Riverside , Riverside, California 92521, United States.
  • Julian RR; Department of Chemistry, University of California-Riverside , Riverside, California 92521, United States.
  • Hooley RJ; Department of Chemistry, University of California-Riverside , Riverside, California 92521, United States.
Inorg Chem ; 56(18): 11435-11442, 2017 Sep 18.
Article en En | MEDLINE | ID: mdl-28841013
Self-assembled Fe-iminopyridine cage complexes containing doubly benzylic methylene units such as fluorene and xanthene can be selectively oxidized at the ligand backbone with tBuOOH, with no competitive oxidation observed at the metal centers. The self-assembled cage structure controls the reaction outcome, yielding oxidation products that are favored by the assembly, not by the reactants or functional groups. Whereas uncomplexed xanthene and fluorene control ligands are solely oxidized to the ketone equivalents with tBuOOH, the unfavorability of the self-assembled ketone cages forces the reaction to form the tbutyl peroxide and alcohol-containing oxidation products, respectively. In addition, the oxidation is diastereoselective, with only single isomers of the cage assemblies formed, despite the presence of as many as 10 stereocenters in the final product. The self-assembled structures exploit self-complementary hydrogen bonding and geometrical constraints to direct the postassembly reactions to outcomes not observed in free solution. This selectivity is reminiscent of the fine control of post-translational modification seen in biomacromolecules.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2017 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos
Texto completo
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Imprimir
XML
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2017 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos