A Mild, Ferrocene-Catalyzed C–H Imidation of (Hetero)Arenes

Formal hydrogen atom abstraction from the nitrogen-hydrogen bonds in purine nucleosides produces reactive intermediates that are important in nucleic acid oxidation. Herein we describe an approach for the independent generation of the purine radical resulting from hydrogen atom abstraction from the N6-amine of 2′-deoxyadenosine (dA•). The method involves sequential Norrish Type I photocleavage of a ketone (7b) and β-fragmentation of the initially formed alkyl radical (8b) to form dA• and acetone. The formation of dA• was followed by laser flash photolysis, which yields a transient with λmax ~ 340 nm and a broader weaker absorption centered at ~560 nm. This transient grows in at ≥ 2 × 105 s−1; however, computations and reactivity data suggest that β-fragmentation occurs much faster, implying the consumption of dA• as it is formed. Continuous photolysis of 7b in the presence of ferrous ion or thiophenol produces good yields of dA, whereas less reactive thiols afford lower yields presumably due to a polarity mismatch. This tandem photochemical, β-fragmentation method promises to be useful for site-specific production of dA• in nucleic acid oligomers and/or polymers and also for the production of aminyl radicals, in general.

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“…In addition, related approaches have been used for generating nitrogen radicals under radical chain conditions. 43,44 …”

Section: Resultsmentioning

confidence: 99%

Aminyl Radical Generation via Tandem Norrish Type I Photocleavage, β-Fragmentation: Independent Generation and Reactivity of the 2′-Deoxyadenosin- N6-yl Radical

et al. 2017

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“…651 The transformation was performed under mild conditions in dichloromethane at 50°C in the presence of ferrocene as catalyst. The process may follow a radical pathway with ferrocene as a single-electron shuttle.…”

Section: Scheme 332mentioning

confidence: 99%

Iron Catalysis in Organic Synthesis

2015

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“…In this way, the C–H imidation used a new perester‐based self‐immolating reagent. Succinimide products obtained were deprotected in situ, giving the corresponding anilines …”

Section: The Ferricinium/ferrocene Redox Shuttle In Catalysismentioning

confidence: 99%

Why is Ferrocene so Exceptional?

2016

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The appearance of ferrocene in the middle of the 20th century has revolutionized organometallic chemistry and is now providing applications in areas as varied and sometimes initially unexpected as optical and redox devices, battery and other materials, sensing, catalysis, including asymmetric and enantioselective catalysis, and medicine. The author presents here a general, although personal, view of ferrocene's chemistry, properties, functions, and applications through a literature survey involving both historical and up‐to‐date trends and including examples of his group's research in a number of these areas. The review gathers together general features of ferrocene chemistry and representative examples of the salient aspects. Its focus is on ferrocene's basic properties, ferrocene‐containing ligands, the ferrocene/ferricinium redox couple, ferrocene mixed‐valence and average‐valence systems, the ferricinium/ferrocene redox shuttle in catalysis, ligand‐exchange reactions, ferrocene‐containing polymers, ferrocene‐containing structures for cathodic battery and other materials, ferrocenes in supramolecular ensembles, liquid crystals, and nonlinear optical materials, ferrocene‐containing stars and their electrostatic effects, ferrocene‐containing dendrons, dendrimers, and nanoparticles (NPs) and their application in redox sensing and catalysis, and ferrocenes in nanomedicine.

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A Mild, Ferrocene-Catalyzed C–H Imidation of (Hetero)Arenes

Cited by 196 publications

References 59 publications

Aminyl Radical Generation via Tandem Norrish Type I Photocleavage, β-Fragmentation: Independent Generation and Reactivity of the 2′-Deoxyadenosin- N6-yl Radical

Aminyl Radical Generation via Tandem Norrish Type I Photocleavage, β-Fragmentation: Independent Generation and Reactivity of the 2′-Deoxyadenosin- N6-yl Radical

Iron Catalysis in Organic Synthesis

Why is Ferrocene so Exceptional?

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