Acyl carbamoyl selenides and related sulfur isologues: synthesis and x‐ray structural analyses

Kageyama, H.; Tani, Kensuke; Katō, Shinzi; Kanda, Takahiro

doi:10.1002/hc.1040

Cited by 14 publications

(2 citation statements)

References 10 publications

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“…Previously, we reported that arenecarbochalcogenoic acids (ArC EE ′H, E = O, S; E ′ = S, Se, Te) react with aryl isocyanates (Ar′NCO) to give the addition products ArC EE ′C(O)NHAr′ ( E = O, S; E ′ = S, Se), the tautomer ArC EE ′C(=NAr′)(OH), which can also be detected spectroscopically 3,5,7a. In fact, ferrocenecarboselenoic acid ( 2 ) was found to readily react with 4‐methylphenyl isocyanate in ether at 25 °C to give the expected (ferrocenoyl)(4‐methylphenylcarbamoyl) selenide ( 5 ) in 94 % yield as red crystals, which showed two characteristic signals at δ = 198.9 and δ = 157.1 in the 13 C NMR spectrum, which can be ascribed to the carbonyl and carbamoyl carbon chemical shifts, respectively.…”

Section: Resultsmentioning

confidence: 99%

Ferrocenecarboselenoic Acid: Synthesis and Some Reactions

Takahashi

Niyomura

Katō

et al. 2012

Zeitschrift anorg allge chemie

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The first ferrocenecarboselenoic acid was synthesized and characterized. The existence of tautomeric equilibrium between the selenol (FcCOSeH) and selenoxo forms (FcCSeOH) in polar solvents was proven by 1 H-, 13 C-and 77 Se-NMR spectra. The selenoxo form exists predominantly in a polar solvent at low temperature below -70°C. Treatment of this acid with lithium, sodium, and potassium hydrides and with rubidium and cesium fluorides gave the corresponding alkali metal ferrocenecarboselenoates in quantitative yields. Treatment with 4-methylphenyl isocyanate at room temperature led to ferro-* Prof. Dr. S. Kato Fax: 81-52-222-2442 E-Mail: kshinzi@nifty.com [a] Faculty of Engineering

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Section: Resultsmentioning

confidence: 99%

Ferrocenecarboselenoic Acid: Synthesis and Some Reactions

Takahashi

Niyomura

Katō

et al. 2012

Zeitschrift anorg allge chemie

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“…However, in spite of their wide application, only a few methodologies have been reported for the preparation of selenocarbamates. These approaches generally rely on the reactivity of isocyanates with selenium‐centered nucleophiles such as selenocarboxylic acids [12] or selenolates, generated by means of reductive cleavage of diselenides with Zn/AlCl 3 [13] . N ‐Alkyl‐ Se ‐alkylselenocarbamates can be prepared from isocyanates and haloalkanes by using LiAlHSeH as the selenating reagent [14] .…”

Section: Introductionmentioning

confidence: 99%

Click Reaction of Selenols with Isocyanates: Rapid Access to Selenocarbamates as Peroxide‐Switchable Reservoir of Thiol‐Peroxidase‐Like Catalysts

et al. 2021

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Selenols react with isocyanates under mild catalyst-free conditions to generate selenocarbamates in good yield and with high selectivity over potentially competing nucleophilic additions. The methodology enables the incorporation of a wide variety of functional groups providing access to a broad array of densely functionalised selenocarbamates. In the presence of competing heteroatom-centered nucleophiles, isocyanates selectively couple with selenols. Selenocarbamates exhibited thiol-peroxidase-like properties, enabling the reduction of hydrogen peroxide at the expense of thiols, which are converted into the corresponding disulfides. A series of control experiments suggested that the catalytic mechanism proceeds through a pathway, involving a H 2 O 2 -promoted transcarbamoylation reaction leading to a thiocarbamate with concomitant releasing of catalytically active selenolate anions. By undergoing peroxide-driven thiol-selenol exchange, selenocarbamates behave as equivalents of selenolate anions with thiol-peroxidase-like activity.

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NMR of Organoselenium and Organotellurium Compounds

Panda

Singh

2012

Patai's Chemistry of Functional Groups

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This chapter gives a systematic account of and surveys the available data on 77 Se and 125 Te NMR spectra of organochalcogen compounds such as chacogenols, mono and dichalcogenides, chalcogenolates, tetra and hexa substituted chalcogen compounds, chalcogenyl halides, chalcogen‐containing heterocycles and macrocycles, chalcogen‐oxygen/nitrogen compounds, etc. The review is based on the literature from 1985 to 2011 and includes 780 references. The 77 Se/ 125 Te NMR spectra of organochalcogen compounds reveal expansive chemical shifts (δ Se /δ Te ) leading to sharp sensitivity of these nuclei (Se/Te) to their environment such as solvent, temperature, molecular geometry, ligand backbone, oxidation state, chelate ring size, steric strain, etc. This is well illustrated by the advantageous use of this spectroscopy in the successful determination of the solution state structure of several organochalcogen compounds. It is noted that the 125 Te and 77 Se chemical shifts of a large number of structurally similar organotellurium and selenium compounds show linear relationship.

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Acyl carbamoyl selenides and related sulfur isologues: synthesis and x‐ray structural analyses

Abstract: Selenocarboxylic acids [RC(‫ס‬O)SeH]were found to readily react with aryl, acyl, and arenesulfonyl

Cited by 14 publications

References 10 publications

Ferrocenecarboselenoic Acid: Synthesis and Some Reactions

Ferrocenecarboselenoic Acid: Synthesis and Some Reactions

Click Reaction of Selenols with Isocyanates: Rapid Access to Selenocarbamates as Peroxide‐Switchable Reservoir of Thiol‐Peroxidase‐Like Catalysts

NMR of Organoselenium and Organotellurium Compounds

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