Anodic Selective Functionalization of Cyclic Amine Derivatives

Onomura, Osamu

doi:10.3987/rev-12-744

Cited by 30 publications

(7 citation statements)

References 99 publications

(16 reference statements)

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“…Similar to aryl amides, the anodic oxidation of alkyl amides or carbamates gives rise to N -centered radical cations. However, these reactive intermediates readily undergo fragmentation to afford N -acyl or N -carbamoyl iminium ions in what is known as the Shono oxidation. , This classic reaction is customarily carried out in an alcoholic solvent with the reactive iminium trapped as an isolable N , O -acetal. This species can revert to an acyliminium upon treatment with acids to allow further functionalizations.…”

Section: Anodic Oxidationmentioning

confidence: 99%

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

2017

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Section: Anodic Oxidationmentioning

confidence: 99%

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

2017

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“…For example, they may be engaged in hydrogenation, 12 cyclopropanation, 13 halogenation, 14 amination, 15 hexannelations 16 and aminoxylation, 17 or allylic functionalization protocols. 18 As detailed in many previous reports, C-2 functionalization of azaheterocycles is achievable when preactivated cyclic enamide precursors such as halides, 19 triflates, [20][21][22] or phosphates 23 are engaged in Suzuki cross-coupling reactions (Fig. 2A).…”

mentioning

confidence: 95%

Regiocontrolled synthesis of (hetero)aryl and alkenyl dehydropyrrolidines, dehydropiperidines and azepenes by Ru-catalyzed, heteroatom-directed α-C–H activation/cross-coupling of cyclic enamides with boronic acids

et al. 2016

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The synthesis of α-aryl and alkenyl pyrrolidine-, piperidine-, and azepane derivatives, through the intermediacy of cyclic enamides is described. The desired outcome is achieved through ruthenium-catalyzed, site-selective sp(2) C-H activation/cross-coupling with aryl and alkenyl boronic acids. The regioselectivity (α-sp(2)vs. α-sp(3)vs. β-sp(2) C-H functionalization) is governed by the rate differences between sp(2) and sp(3) C-H activation and the necessity for chelation between the ruthenium metal and the carbonyl directing group.

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“…In electro‐organic synthesis, modified electrodes offer experimental tools for immobilisation of catalysts, induction of chirality, or improved selectivity and enhanced catalytic reactivity . In particular microporous films have been developed and coated onto electrodes to aid electrochemical processes based on zeolites, ceramic hybrids, metal‐organic frameworks, porous organic cages, and a wide range of polymers .…”

Section: Introductionmentioning

confidence: 99%

Polymer of Intrinsic Microporosity (PIM‐7) Coating Affects Triphasic Palladium Electrocatalysis

et al. 2018

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A film of the polymer of intrinsic microporosity PIM‐7 is coated onto a glassy carbon electrode and the resulting effects on electron transfer reactions are studied for three different types of processes: (i) aqueous solution based, (ii) solid state surface immobilised, and (iii) electrocatalytic processes on electrodeposited palladium. The effects on reactivity for hydroquinone oxidation in aqueous phosphate buffer are shown to be linked to microporosity causing a slightly lower rate of mass transport without detrimental effects on electron transfer and reaction kinetics. Next, water‐insoluble microcrystalline anthraquinone is immobilised directly into the PIM‐7 film and shown to give a chemically reversible reduction process, which is enhanced in the presence of PIM‐7, when compared to the case of anthraquinone immobilised directly onto bare glassy carbon. Electrodeposition of a film of nano‐palladium is demonstrated to give catalytically active electrodes for the reduction/oxidation of protons/hydrogen, the reduction of oxygen, and for the oxidation of formic acid and methanol. With the PIM‐7 film applied onto palladium, a mechanical stabilisation effect occurs. In addition, both the hydrogen insertion and the hydrogen evolution reactions as well as formic acid oxidation are enhanced. Effects are discussed in terms of PIM‐7 beneficially affecting the interfacial reaction under triphasic conditions. The microporous polymer acts as an interfacial “gas management” layer.

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Anodic Selective Functionalization of Cyclic Amine Derivatives

Cited by 30 publications

References 99 publications

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Regiocontrolled synthesis of (hetero)aryl and alkenyl dehydropyrrolidines, dehydropiperidines and azepenes by Ru-catalyzed, heteroatom-directed α-C–H activation/cross-coupling of cyclic enamides with boronic acids

Polymer of Intrinsic Microporosity (PIM‐7) Coating Affects Triphasic Palladium Electrocatalysis

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