An Improved Catalyst for Iodine(I/III)‐Catalysed Intermolecular CH Amination

Lucchetti, Nicola; Scalone, Michelangelo; Fantasia, Serena; Muñiz, Kilian

doi:10.1002/adsc.201600191

Cited by 38 publications

(21 citation statements)

References 94 publications

(10 reference statements)

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“…Catalyst 3b was used as the aryl iodide mediator due to its previously reported success in furnishing intermolecular C-H amination reactions (see Table S6 for analysis of other aryl iodide catalysts). 20 CPE in the presence of 1 equivalent of 3b affords 81% yield of Nphenylated compound 5a and the loading can be decreased to 25 mol% without significantly depressing the yield (71% of isolated product). Similar to the above-described intramolecular C-N bond-forming chemistry, no C-N coupling products are observed in the absence of either aryl iodide or [TBA]OAc.…”

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confidence: 99%

Electrocatalytic C–N Coupling via Anodically Generated Hypervalent Iodine Intermediates

et al. 2020

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Development of new electrosynthetic chemistry promises to impact the efficiency and sustainability of organic synthesis. Here we demonstrate that anodically generated hypervalent iodine intermediates effectively couple interfacial electron transfer with oxidative C-H/N-H coupling chemistry. The developed hypervalent iodine electrocatalysis is applicable in both intraand intermolecular C-N bond-forming reactions. Available mechanistic data indicates that anodic oxidation of aryl iodides generates a transient I(II) intermediate that is critically stabilized by added acetate ions. This report represents the first example of metal-free hypervalent iodine electrocatalysis for C-H functionalization and provides mechanistic insight that we anticipate will contribute to the development of hypervalent iodine mediators for synthetic electrochemistry.Electrochemistry is an attractive approach to sustainable synthesis that obviates the need for stoichiometric redox reagents and thus, generation of the attendant waste streams. 1 Due to its inherent tunability and scalability, electrosynthesis should impact many of the enormous variety of organic transformations in which electrons are added to, or removed from, substrates. In practice, challenges such as 1) the sluggish interfacial electron transfer rates for many organic molecules, which necessitates application of substantial overpotential to achieve practical current densities, 2 and 2) the need to couple the single-electron events that are typical of electrochemistry with the multi-electron events required for bond-breaking and -making in organic reactions, can

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confidence: 99%

Electrocatalytic C–N Coupling via Anodically Generated Hypervalent Iodine Intermediates

et al. 2020

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“…In 2016, Muñiz et al developed an iodine(III)‐based catalytic system for intermolecular N−H arylation involving a nitrenium ion (Figure ) . 1,2‐Diiodobenzene was used as a precatalyst in the presence of peracetic acid as oxidant.…”

Section: C−n Bond Formation Reactionsmentioning

confidence: 82%

Nitrenium Ions from Amine‐Iodine(III) Combinations

et al. 2019

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Hypervalent iodine compounds are known for their extensive use as potentialo xidants in organic synthesis.I ns pite of the similar reactivity with transitionm etals,h ypervalent iodine reagents are more preferred because of their environmental sustainability.A mong several types of hypervalent iodine reagents,t rivalent organoiodine(III) reagents are highly popular due to their easy accessibility,s tability and controlled oxidizing reactivity.A lso, iodine(III) reagents are commerciallya vailable andi nexpensive. Amines and amidesr eact with iodine(III) oxidants in some specificw ay to provide ad ivalent electrophilic ionic species known as an itrenium ion. Depending on the nature and stability of the nitrenium ion, numerous oxidative transformations to generate valuable functional molecules have been reported.T his review encompassesd iscussionsa bout hypervalent organo iodine(III)-enabled organic transformationsw ith the involvemento fanitrenium ion as an intermediate. Figure1.Ionic electrophilic speciesw ith 6v alance electrons.

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“…Subjecting Chem. [61] 2016, 22,15584 -15598 www.chemeurj.org N,N-diphthalimidoiodane 7 to the reactionc onditions afforded 38 %y ield and comparable regioselectivity to the parent reaction, thus demonstrating that the iodane 7 is chemically competent.…”

Section: Carbon-nitrogen Bondsmentioning

confidence: 89%

Recent Advances in Gold‐Catalyzed Intermolecular Aryl C−H Functionalization

Kramer

2016

Chemistry A European J

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The direct and selective functionalization of C-H bonds offers a powerful opportunity for greener and shorter routes to valuable chemicals. While still in its infancy, research exploiting the unique features of gold catalysis for the functionalization of aryl C-H bonds has demonstrated great potential for facile regioselective decoration of (hetero)arenes. Particularly within the last five years, a more general strategy for utilizing oxidative gold catalysis has emanated including an improved understanding of the underlying mechanistic pathways. To encourage and facilitate further research in intermolecular C-H functionalization of arenes with homogeneous gold catalysis, this Minireview critically presents the transformations and mechanistic data available within this field.

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An Improved Catalyst for Iodine(I/III)‐Catalysed Intermolecular CH Amination

Cited by 38 publications

References 94 publications

Electrocatalytic C–N Coupling via Anodically Generated Hypervalent Iodine Intermediates

Electrocatalytic C–N Coupling via Anodically Generated Hypervalent Iodine Intermediates

Nitrenium Ions from Amine‐Iodine(III) Combinations

Recent Advances in Gold‐Catalyzed Intermolecular Aryl C−H Functionalization

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