- Green Synthesis of Diaryl Selenides from Arylboronic Acids and Arylseleninic Acids
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A new method of deborylative selanylation using arylboronic acids and arylseleninic acids gave diaryl selenoethers and diarylselenoxide. The present approach requires only equimolar arylseleninic acid and led selectively to selenoethers or selenoxides depending on the solvent. The method is metal-free, base- or oxidant-free, efficient, and environmentally friendly.
- Redon, Sébastien,Remusat, Vincent,Vanelle, Patrice
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supporting information
p. 483 - 487
(2022/02/21)
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- Visible light-induced photodeoxygenation of polycyclic selenophene Se-oxides
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Photodeoxygenation of dibenzothiophene S-oxide (DBTO) is believed to produce ground-state atomic oxygen [O(3P)] in solution. Compared with other reactive oxygen species (ROS), O(3P) is a unique oxidant as it is potent and selective. Derivatives of DBTO have been used as O(3P)-precursors to oxidize variety of molecules, including plasmid DNA, proteins, lipids, thiols, and other small organic molecules. Unfortunately, the photodeoxygenation of DBTO requires ultraviolet irradiation, which is not an ideal wavelength range for biological systems, and has a low quantum yield of approximately 0.003. In this work, benzo[b]naphtho[1,2-d]selenophene Se-oxide, benzo[b]naphtho[2,1-d]selenophene Se-oxide, dinaphtho[2,3-b:2’,3’-d]selenophene Se-oxide, and perylo[1,12-b,c,d]selenophene Se-oxide were synthesized, and their ability to utilize visible light for generating O(3P) was interrogated. Benzo[b]naphtho[1,2-d]selenophene Se-oxide produces O(3P) upon irradiation centered at 420 nm. Additionally, benzo[b]naphtho[1,2-d]selenophene Se-oxide, benzo[b]naphtho[2,1-d]selenophene Se-oxide, and dinaphtho[2,3-b:2’,3’-d]selenophene Se-oxide produce O(3P) when irradiated with UVA light and have quantum yields of photodeoxygenation ranging from 0.009 to 0.33. This work increases the utility of photodeoxygenation by extending the range of wavelengths that can be used to generate O(3P) in solution.
- Chintala, Satyanarayana M.,Throgmorton, John C.,Maness, Peter F.,McCulla, Ryan D.
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supporting information
(2020/10/02)
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- ORGANODIARYL SELENOXIDES AND PROCESS FOR PREPARATION THEREOF
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Novel organodiaryl selenoxides and processes for preparation thereof, and use thereof as ligand in complexes.
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Paragraph 0129-0132
(2017/06/29)
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- Oxidation of sulfides using recyclable pseudocyclic benziodoxole triflate
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A new pseudocyclic hypervalent iodine reagent, benziodoxole triflate (IBA-OTf, a complex of 2-iodosylbenzoic acid with trifluoromethanesulfonic acid), can be used as an efficient oxidant for selective oxidation of various organic sulfides to sulfoxides. This oxidation proceeds under mild condition to afford the corresponding sulfoxides in moderate to good yields without overoxidation. The reduced form of the hypervalent iodine reagent, 2-iodobenzoic acid, can be easily recovered from the reaction mixture in good yields by a simple acid-base liquid-liquid biphasic protocol. (Chemical Equation Presented).
- Yoshimura, Akira,Zhdankin, Viktor V.
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- Synthesis of 9-oxoselenoxanthenium and triarylselenonium hexafluorophosphates
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The selenoxides forming 9-oxoselenoxanthenium and triaryl selenonium hexafluorophosphates via interaction with heptyl phenyl ether and anisole in the MeSO3H-P2O5 mixture followed by treatment with KPF6 have been obtained via selenoxantene-9-one and diphenyl selenide derivatives oxidation with m-chloroperoxybenzoic acid or hydrogen peroxide.
- Loskutov,Balina,Russkikh,Shelkovnikov
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p. 1093 - 1097
(2015/06/30)
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- Lewis basic selenium catalyzed chloroamidation of olefins using nitriles as the nucleophiles
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A Lewis base catalyzed chloroamidation of olefinic substrates was achieved using diphenyl selenide as the catalyst. The reaction conditions are mild and suitable for a wide range of substrates including those which are acid labile.
- Tay, Daniel Weiliang,Tsoi, Ivan Tan,Er, Jun Cheng,Leung, Gulice Yiu Chung,Yeung, Ying-Yeung
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p. 1310 - 1313
(2013/04/24)
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- A general and efficient method to convert selenides into selenones by using HOF·CH3CN
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A general route for the preparation of selenones (R2SeO 2) is presented. This task is achieved through the quick and high-yielding reaction of selenides (R2Se) with HOF·CH 3CN. The reaction tolerates some elusiv
- Potash, Shay,Rozen, Shlomo
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p. 5574 - 5579
(2013/09/12)
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- Aqueous sodium hypochlorite mediated chemoselective oxidation of chalcogenides to monoxides and dioxides by microwave exposure
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A solvent-free, rapid, and highly selective oxidation of sulfides, selenides, and tellurides (chalcogenides) to the corresponding monoxides (sulfoxides, selenoxides, and telluroxides) or the corresponding dioxides (sulfones, selenones, and tellurones) has been developed using aqueous sodium hypochlorite on solid supports by exposure to microwave. Chemoselectivity and quantitative yields have been attained in most cases.
- Khurana, Jitender,Nand, Bhaskara
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experimental part
p. 906 - 909
(2011/01/08)
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- Deoxygenation and other photochemical reactions of aromatic selenoxides
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Atomic oxygen O(3P) is a potent oxidant that has been well-studied in the gas phase. However, exploration of its reactivity in the condensed organic phase has been hampered by the lack of an appropriate source. Dibenzothiophene-S-oxide (DBTO) and related derivatives have been promoted as photochemical D(3P) sources but suffer from low quantum yields. Photolysis of dibenzoselenophene-Se-oxide (DBSeO) results in the formation of dibenzoselenophene and oxidized solvent in significantly higher quantum yields, ca. 0.1. The oxidation product ratios from toluene obtained from the photolysis of dibenzothiophene-S-oxide and the corresponding selenoxide are the same, strongly suggesting a common oxidizing intermediate, which is taken to be O(3P). An additional product, proposed to be the corresponding selenenic ester, is also observed under deoxygenated conditions. The photochemistry of diphenyl selenoxide includes a minor portion of oxidant-forming deoxygenation, in contrast to previous conclusions.
- McCulla, Ryan D.,Jenks, William S.
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p. 16058 - 16065
(2007/10/03)
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- Singlet oxygen oxidation of selenides to selenoxides
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The presence of water and a carbonate proved to be highly beneficial for singlet oxygen oxidation of selenides to selenoxides.
- Krief, Alain,Lonez, Frédéric
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p. 6255 - 6257
(2007/10/03)
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- Reactions of alkynylselenonium salts with tetrabutylammonium halides: Apparent umpolung of alkynyl moiety
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The reactions of alkynylselenonium salts with n-Bu4NX (X = I, Br, Cl) in CH2Cl2 gave 1-halo-1-alkynes or phenacyl halide derivatives and selenide, while the reaction with F afforded a terminal alkyne and a selenoxide. Seemingly, the selenonium salts acted as alkynyl cations in the former case and as alkynyl anions in the latter case.
- Kataoka, Tadashi,Watanabe, Shin-ichi,Yamamoto, Keiichirou
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p. 931 - 934
(2007/10/03)
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- Reactions of Diphenyl(phenylethynyl)selenonium Salts with Active Methylene Compounds and Amides: First Isolation of Oxyselenuranes [10-Se-4(C3O)] as a Reaction Intermediate
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The reaction of the diphenyl(phenylethynyl)selenonium triflate 1a with active methylene compounds 5 and t-BuOK in THF gave furan derivatives 6. The [10-Se-4(C3O)l selenuranes 8a and 8b could be isolated from the reactions with benzoylacetonitrile 5f and with 1,3-indandione 5g, respectively, as reaction intermediates. The structures of the selenuranes 8 were elucidated by X-ray crystallography and 77Se high-resolution solid-state NMR spectroscopy. The selenuranes 8 underwent ligand coupling on standing at room temperature or refluxing in chloroform and gave the furan derivatives 6 and the ring-opened product 9. Similarly, the reaction of 1a with benzamide 13a and pivalamide 13d in the presence of NaH in THF afforded oxazole derivatives 14.
- Kataoka, Tadashi,Watanabe, Shin-Ichi,Yamamoto, Keiichirou,Yoshimatsu, Mitsuhiro,Tanabe, Genzoh,Muraoka, Osamu
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p. 6382 - 6386
(2007/10/03)
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- A Mechanism for the Oxidation of Glutathione to Glutathione Disulfide with Organotellurium(IV) and Organoselenium(IV) Compounds. A Stepwise Process with Implications for Photodynamic Therapy and Other Oxidative Chemotherapy
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The reactions of telluroxides or their hydrates 3-5 with glutathione to give telluropyrylium dyes 1,2 or diphenyl telluride, respectively, and glutathione disulfide have at least two discrete steps.A fast reaction, which is first-order in both substrate and glutathione, is observed with second-order rate constants of 2.30E7 L mol-1 s-1 at 285.4 K for 3, 1.66E7 L mol-1 s-1 at 293.2 K for 4, and 5.2E6 L mol-1 s-1 at 285.5 K for 5.This reaction is followed by a slower reaction, which is first-order in both substrate and glutathione, with second-order rate constants of 2.65E5 L mol-1 s-1 at 293.5 K for 3, 3.34E5 L mol-1 s-1 at 293.2 K for 4, and 7.64E3 L mol-1 s-1 at 285.5 K for 5.The slow reaction is accompanied by the generation of the corresponding tellurium(II) compound.Diphenyl selenoxide hydrate (6) displays similar behavior, although the rate constants associated with the fast (2.26E2 L mol-1 s-1) and slow (6.62E1 L mol-1 s-1) reactions are many orders-of-magnitude less than observed for the tellurium analogues.
- Detty, Michael R.,Friedman, Alan E.,Oseroff, Alan R.
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p. 8245 - 8250
(2007/10/02)
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- Extremely Facile Ligand-Exchange and Disproportionation Reactions of Diaryl Sulfoxides, Selenoxides, and Triarylphosphine Oxides with Organolithium and Grignard Reagents
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Diaryl sulfoxides undergo unusually rapid ligand-exchange reaction upon treatment with organolithium reagents at -95 deg C.Optically pure phenyl p-tolyl sulfoxide (4b) reacted with organolithium reagents at the range from -20 to -95 deg C to give facile ligand-exchange and disproportionation products, i.e., diphenyl sulfoxide (7), recovered 4b, and di-p-tolyl sulfoxide (8) in a statistical ratio of 1:2:1 in quantitative yields, and the recovered 4b was completely racemized.This facile ligand exchange was observed in the similar reactions using only diaryl selenoxides and triarylphosphine oxides.The reactions of 18O-labeled phenyl p-tolyl sulfoxide (4c) with organolithium reagents gave products in a statistical ration without 18O scrambling, indicating that only the C-S bond cleavage took place under low temperature.It is suggested that the ligand exchange reactions occur by the nucleophilic attack by organolithium reagent at the sulfinyl sulfur atom, giving ?-sulfurane as an intermediate that collapses rapidly.These results suggest that the treatment of arylic sulfoxides, selenoxides, and phosphine oxides with strong bases should be effected with caution.
- Furukawa, Naomichi,Ogawa, Satoshi,Matsumura, Kazunori,Fujihara, Hisashi
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p. 6341 - 6348
(2007/10/02)
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- SYNTHESIS, STRUCTURE, AND CHARACTERISTICS OF COMPOUNDS WITH A CHALCOGEN-NITROGEN BOND. IX. REACTION OF N-SULFONYLSELENIMIDES WITH AROMATIC ALDEHYDES
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N-Sulfonylselenimides enter into reaction with aromatic aldehydes leading to the formation of N-sulfonylazomethines.This reaction forms the basis of the catalytic action of selenimides during the condensation of aldehydes with sulfonamides.
- Naddaka, V. I.,Avanesyan, K. V.,Cherkinskaya, M. L.,Minkin, V. I.
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p. 1154 - 1156
(2007/10/02)
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- PREPARATION AND REACTION OF N-TOSYL- AND N-ACYLSELENILIMINES
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N-Tosyl-Se,Se-diphenylselenilimines (Ia, hydrate state (Ib) of Ia), N-tosyl-Se-methyl-Se-phenylselenilimines (Ic), N-tosyl-Se,Se-dialkylselenilimines (Id-f), N-acyl-Se-aryl-Se-phenyl-selenilimines (IIa-e) and N-acyl-Se,Se-dibenzylselenilimine (IIf) were prepared.The pyrolyses of selenilimines (Ia, d, e, IIa-e) proceeded more readily than those of the corresponding sulfur derivatives.The pyrolyses of N-acyl-Se-aryl-Se-phenylselenilimines gave the corresponding isocyanates in good yields after treatment of the reaction mixture with aniline, together with aryl phenyl selenide.A ki netic study revealed that the rate of pyrolysis of N-benzoyl-Se,Se-diphenylselenilimine (IIa) was 300 times faster than that of the corresponding sulfilimine.The activation enthalpy and entropy were ΔH* = 32.1 kcal/mol and ΔS* = 1.2 e.u. respectively for Ph2Se -> NCOPh.Oxidations of N-tosyl- and N-benzoyl-Se,Se-diphenylselenilimine were carried out with hydrogen peroxide or potassium permanganate to obtain the corresponding selenoxides or selenones, respectively.Hydrolysis of N-tosyl- and N-benzoyl-Se,Se-diphenylselenilimines also took place more readily than that of the corresponding sulfilimines and the selenoxides and the amides were obtained in good yields at room temperature.When N-tosyl-Se,Se-pentamethyleneselenilimine (Ie) was treted with conc. sulfuric acid, a selenurane, Se-hydroxy-Se-(hydroxysulfoxy)selenane (III) was obtained in a high yield.
- Oae, Shigeru,Fukumura, Mitsuo,Furukawa, Naomichi
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p. 153 - 162
(2007/10/02)
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- Oxidation of Selenides and Tellurides with Positive Halogenating Species
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Treatment of diaryl or alkyl aryl selenides and diaryl or dialkyl tellurides first with a positive halogen source (N-chlorosuccinimide, tert-butyl hypochlorite) followed by alkaline hydrolysis (10percent sodium hydroxide, saturated sodium bicarbonate) gave the corresponding selenoxides or telluroxides (or hydrates) in good yield.The method is tolerant of a variety of functional groups including esters, olefins, alcohols, ethers, and ketones.The formal oxidation step is believed to be the formation of a chloroselenonium or chlorotelluronium species followed by hydrolysis. 1H NMR evidence is given for a benzylphenylselenonium species. Selenoxide fragmentation reactions during the hydrolysis step were observed
- Detty, Michael R.
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p. 274 - 279
(2007/10/02)
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