- Selective difluoroalkylation of alkenes by using visible light photoredox catalysis
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A visible light-induced process for selective difluoroalkylation of unactivated alkenes has been developed. The choice of base is crucial for governing the chemoselectivity of the process to produce difluoroalkylated alkanes and alkenes. This journal is
- Yu, Chunghyeon,Iqbal, Naeem,Park, Sehyun,Cho, Eun Jin
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- The activation of carbon-chlorine bonds in per- and polyfluoroalkyl chlorides: DMSO-induced hydroperfluoroalkylation of alkenes and alkynes with sodium dithionite
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In DMSO, the addition reactions of perfluoroalkyl chlorides, R(F)Cl, to alkenes or alkynes can occur smoothly in the presence of 1.5 equiv of Na2S2O4 and NaHCO3 at 75-80 °C for 4-10 h to give the corresponding adducts (RCH2CH2RF or RCH = CHR(F)). Ethyl chlorofluoro- (1f), chlorodifluoro- (1g) acetates, even nonfluorinated compounds, such as ethyl dichloro- (1h), chloro- (1i) acetates, and chloroform (1j) can undergo the similar reaction. Treatment of ω-iodo (or chloro-) perfluoroalkyl chlorides [X(CF2)(n) Cl, n = 2, 4, X= I or Cl] with > 3 equiv of alkenes and Na2SO4 gives directly the symmetrically disubstituted alkanes (RCH2CH2)2(CF2)(n). The symmetrically and unsymmetrically disubstituted adducts RCH2CH2(CF2)(n)CH2CH2R' from ω-iodoperfluoroalkyl chlorides can be also obtained stepwise, i.e., through the further addition reactions of monoadducts, RCH2CH2(CF2)(n)Cl to olefins. However, for α,ω- dichloroperfluoroalkanes, the similarly stepwise reactions with an alkene is not clean, both bis-adducts and the corresponding ω-hydrides, RCH2CH2(CF2)(n)H as byproducts are also formed. In the absence of alkenes or alkynes, per- and polyfluoroalkyl chlorides can be converted to their sulfinate salts and sulfonyl chlorides.
- Long, Zheng-Yu,Chen, Qing-Yun
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- Photoredox-Catalyzed Hydrodifluoroalkylation of Alkenes Using Difluorohaloalkyl Compounds and a Hantzsch Ester
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Photoredox-catalyzed hydrodifluoroalkylation of alkenes proceeded smoothly in the presence of a Hantzsch ester as a hydrogen source under visible light irradiation. The reaction was also applicable to the hydrodifluoroalkylation of alkynes, and a continuous photo flow reaction was also successful.
- Sumino, Shuhei,Uno, Misae,Fukuyama, Takahide,Ryu, Ilhyong,Matsuura, Makoto,Yamamoto, Akinori,Kishikawa, Yosuke
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p. 5469 - 5474
(2017/05/24)
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- As opioid receptor antagonists or inverse agonists of the novel compounds
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Novel compounds which are antagonists or inverse agonists at one or more of the opioid receptors, pharmaceutical compositions containing them, to processes for their preparation.
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Paragraph 0275; 0276
(2016/10/08)
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- NOVEL COMPOUNDS AS ANTAGONISTS OR INVERSE AGONISTS AT OPIOID RECEPTORS
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Novel compounds which are antagonists or inverse agonists at one or more of the opioid receptors, pharmaceutical compositions containing them, to processes for their preparation.
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- METHOD OF TREATMENT USING NOVEL ANTAGONISTS OR INVERSE AGONISTS AT OPIOID RECEPTORS
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A method of treatment using pharmaceutical compositions containing novel antagonists or inverse agonists at opioid receptors for the treatment of binge eating disorder, anorexia nervosa, bulimia nervosa, excess drug or alcohol use, or eating disorder not otherwise specified.
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- CHEMICAL COMPOUNDS
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The invention relates to chemical compounds, or pharmaceutically acceptable salts thereof of the formula which possess CSF 1R kinase inhibitory activity and are accordingly useful for their anti cancer activity and thus in methods of treatment of the human or animal body. The invention also relates to processes for the manufacture of said chemical compounds, to pharmaceutical compositions containing them and to their use in the manufacture of medicaments of use in the production of an anti-cancer effect in a warm blooded animal such as man.
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Page/Page column 57
(2008/06/13)
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- Photochemical generation of difluoromethyl radicals having various functional groups and their highly regioselective addition to olefins and aromatic substitution
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Difluoromethyl radicals bearing ester, phosphonate, nitrile, cyclic carbonate, and carbamate groups were generated by the photoinitiated S-CF2 bond cleavage of electrosynthesized α,α-difluorosulfides, and their addition to olefins and aromatic substitution were successfully carried out to provide the regioselective adducts and substitution products in moderate yields. The yields of substitution products increased by the addition of diphenyl diselenide and 2,4,6-trimethylpyridine.
- Nagura, Hirokatsu,Murakami, Satoru,Fuchigami, Toshio
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p. 10237 - 10245
(2008/02/13)
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- Electrosynthesis of ethyl α, α-difluoro-α-(phenylseleno)acetate and its photochemical synthetic application
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Anodic fluorination of ethyl α-fluoro-α-(phenylseleno) acetate was successfully carried out to give ethyl α,α -difluoro-α-(phenylseleno)acetate in high yield. Photolysis of the difluorinated product in the presence of various olefins provided regioselective difluorometylene adducts in good to moderate total yields. The reaction involves phenylselenyl transfer at the early stage followed by the elimination of a phenylselenyl group from the adducts once formed to provide the unsaturated and saturated difluoromethylene products.
- Murakami, Satoru,Ishii, Hideki,Fuchigami, Toshio
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p. 609 - 614
(2007/10/03)
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- A New Approach to α,α-Difluoro-Functionalized Esters
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The addition reaction of iododifluoroacetates to alkenes is initiated by copper powder (10-20 mol percent) at 50-60 deg C.Both terminal and internal alkenes give good yields of adducts.The reaction is also applicable to alkenes containing a variety of functional groups, such as epoxy, hydroxy, ketone, ester, and phosphonate moieties.This reaction can be carried out either neat or in solvents such as hexane, benzene, acetonitrile, DMF, DMSO, and HMPA and is suppressed by p-dinitrobenzene and di-tert-butyl nitroxide.A single electron transfer initiated radical mechanism isproposed.In the presence of nickel dichloride hexahydrate, reduction of the adducts with zinc in moist THF provides the corresponding α,α-difluoro esters in good yields.
- Yang, Zhen-Yu,Burton, Donald J.
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p. 5125 - 5132
(2007/10/02)
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