Journal ArticleDOI
Supramolecular Recognition Allows Remote, Site-Selective C−H Oxidation of Methylenic Sites in Linear Amines
Giorgio Olivo,Giulio Farinelli,Alessia Barbieri,Osvaldo Lanzalunga,Stefano Di Stefano,Miquel Costas +5 more
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TLDR
A supramolecular, bioinspired approach is described to address site-selective C-H functionalization of aliphatic alkyl chains in oxidation catalysis, overriding the intrinsic reactivity of C- H bonds, no matter the chain length.Abstract:
Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp3 )-H hydroxylation with H2 O2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length.read more
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A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry.
Carlo Sambiagio,David Schönbauer,Remi Blieck,Toan Dao-Huy,Gerit Pototschnig,Patricia Schaaf,Thomas Wiesinger,Muhammad Farooq Zia,Joanna Wencel-Delord,Tatiana Besset,Bert U. W. Maes,Michael Schnürch +11 more
TL;DR: The present review is devoted to summarizing the recent advances (2015–2017) in the field of metal-catalysed group-directed C–H functionalisation.
Journal ArticleDOI
Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C-H Bonds Elaboration
TL;DR: A comprehensive review of the synthetic applications of photocatalyzed d-HAT can be found in this article, where the authors provide a comprehensive overview of the main applications of PCHAT.
Journal ArticleDOI
Selective C(sp3)−H aerobic oxidation enabled by decatungstate photocatalysis in flow
Gabriele Laudadio,Sebastian Govaerts,Ying Wang,Davide Ravelli,Hannes Fiepko Koolman,Hannes Fiepko Koolman,Maurizio Fagnoni,Stevan W. Djuric,Timothy Noël +8 more
TL;DR: In this paper, a mild and selective C(sp3 )-H aerobic oxidation enabled by decatungstate photocatalysis has been developed, which allows for the oxidation of both activated and unactivated C-H bonds.
Selective sp3 C–H aerobic oxidation enabled by decatungstate photocatalysis in flow
TL;DR: A mild and selective C(sp3)−H aerobic oxidation enabled by decatungstate photocatalysis has been developed and the reaction can be significantly improved in a microflow reactor enabling the safe use of oxygen and enhanced irradiation of the reaction mixture.
Journal ArticleDOI
Enantioselective Radical Reactions Using Chiral Catalysts.
TL;DR: A comprehensive review of progress in enantioselective radical reactions with a goal of detailing the reaction mechanisms involved in these transformations such that any nonspecialist could find their own creativity to invent yet unknown applications is provided in this article .
References
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Journal ArticleDOI
Thermodynamic and kinetic data for macrocycle interactions with cations and anions
Journal ArticleDOI
If C-H bonds could talk: selective C-H bond oxidation.
TL;DR: The perspective taken herein will allow C-H oxidation reactions to be more readily incorporated into synthetic planning and to emphasize chemoselectivity imposed by the nature of the substrate.
Journal ArticleDOI
A Predictably Selective Aliphatic C-H Oxidation Reaction for Complex Molecule Synthesis
Mark S. Chen,M. Christina White +1 more
TL;DR: An iron (Fe)–based small molecule catalyst that uses hydrogen peroxide (H2O2) to oxidize a broad range of substrates and Predictable selectivity is achieved solely on the basis of the electronic and steric properties of the C–H bonds, without the need for directing groups.
Journal ArticleDOI
Combined effects on selectivity in Fe-catalyzed methylene oxidation.
Mark S. Chen,M. Christina White +1 more
TL;DR: It is reported that an iron catalyst can achieve methylene C–H bond oxidations in diverse natural-product settings with predictable and high chemo-, site-, and even diastereoselectivities.
Journal ArticleDOI
Undirected, Homogeneous C-H Bond Functionalization: Challenges and Opportunities.
TL;DR: This outlook discusses future directions for research on undirected C–H functionalization, with an emphasis on the limitations that must be overcome if this type of methodology is to become widely used in academia and in industry.
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A Predictably Selective Aliphatic C-H Oxidation Reaction for Complex Molecule Synthesis
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