- Vinylation of Iododifluoromethylated Alcohols via a Light-Promoted Intramolecular Atom-Transfer Reaction
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A method for the synthesis of gem -difluorohomoallylic alcohols by the substitution of iodine in the iododifluoromethyl group by a vinyl fragment is described. The reaction proceeds via an intramolecular iodine atom transfer followed by β-elimination. The reaction is performed in the presence of an iridium photocatalyst, fac -Ir(ppy) 3, and triphenylphosphine under irradiation with light-emitting diodes.
- Panferova, Liubov I.,Struchkova, Marina I.,Dilman, Alexander D.
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p. 4124 - 4132
(2017/09/12)
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- Supported gold nanoparticles catalyzed: Cis -selective semihydrogenation of alkynes using ammonium formate as the reductant
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TiO2 supported gold nanoparticles with low loading (0.5 mol%) are able to semihydrogenate non-fluorinated and gem-difluorinated alkynes to cis-alkenes with high selectivity, using cost-effective and easy-to-handle ammonium formate as the reductant. No over-reduction was observed. The good recyclability of Au/TiO2 allows for "green" semireduction of alkynes. A difluorinated pyran and α,β-unsaturated δ-lactone were easily prepared from the obtained gem-difluoro alkene building blocks.
- Liang, Shengzong,Hammond, Gerald B.,Xu, Bo
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p. 6013 - 6016
(2016/05/24)
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- Rh-catalyzed allylic C-F bond activation: The stereoselective synthesis of trisubstituted monofluoroalkenes and a mechanism study
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Rhodium-catalyzed allylic C-F bond activation via oxidative addition was found to be a promising approach for the conversion of allylic difluoro-homoallylic alcohols into trisubstituted monofluoroalkenes in good yields with excellent stereoselectivity. The mechanism study shows that C-F bond activation via oxidative addition is involved and PPh3 is responsible for the excellent stereoselectivity. The Royal Society of Chemistry.
- Zhang, He,Lin, Jin-Hong,Xiao, Ji-Chang,Gu, Yu-Cheng
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p. 581 - 588
(2014/01/06)
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- B -(3,3-Difluoroallyl)diisopinocampheylborane for the enantioselective fluoroallylboration of aldehydes
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The fluoroallylboration of aldehydes with B-(3,3-difluoroallyl) diisopinocampheylborane, which was prepared via the hydroboration of 1,1-difluoroallene, provides chiral 2,2-gem-difluorinated homoallylic alcohols in good yields and 91-97% ee.
- Ramachandran, P. Veeraraghavan,Tafelska-Kaczmarek, Agnieszka,Chatterjee, Anamitra
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p. 9329 - 9333,5
(2012/12/11)
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- B -(3,3-Difluoroallyl)diisopinocampheylborane for the enantioselective fluoroallylboration of aldehydes
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The fluoroallylboration of aldehydes with B-(3,3-difluoroallyl) diisopinocampheylborane, which was prepared via the hydroboration of 1,1-difluoroallene, provides chiral 2,2-gem-difluorinated homoallylic alcohols in good yields and 91-97% ee.
- Ramachandran, P. Veeraraghavan,Tafelska-Kaczmarek, Agnieszka,Chatterjee, Anamitra
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p. 9329 - 9333
(2013/01/15)
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- Synthesis of 4,4-difluoroglycosides using ring-closing metathesis
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4-Deoxy-4,4-difluoro-glycosides have been synthesised for the first time via a direct sequence involving ring-closing metathesis and indium-mediated difluoroallylation with 1-bromo-1,1-difluoropropene in water. Two protecting group strategies were explore
- Audouard, Christophe,Fawcett, John,Griffiths, Gerry A.,Percy, Jonathan M.,Pintat, Stephane,Smith, Clive A.
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p. 528 - 541
(2007/10/03)
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- Indium-mediated reaction of 3-bromo-3,3-difluoropropene and bromodifluoromethylacetylene derivatives with aldehydes
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Aldehydes reacted with 3-bromo-3,3-difluoropropene at the α-position in the presence of indium to afford 1-substituted-2,2-difluorobut-3-en-1-ols. Ketones and other electrophiles are inert under the examined conditions. The reaction of bromodifluoromethyl
- Kirihara, Masayuki,Takuwa, Tomofumi,Takizawa, Shinobu,Momose, Takefumi,Nemoto, Hideo
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p. 8275 - 8280
(2007/10/03)
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- Rapid syntheses of difluorinated dihydropyrans
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A very short reaction sequence opens with metal-mediated addition of commercial bromodifluoropropene to aldehydes; allylation under phase transfer catalysed conditions sets the stage for a ring closing metathesis (RCM) in the presence of commercial Grubbs
- Percy, Jonathan M.,Pintat, Stephane
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p. 607 - 608
(2007/10/03)
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- The addition of dibromodifluoromethane to (trimethylsilyl)acetylene and transformation of the products
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Reaction of dibromodifluoromethane (1) with (trimethylsilyl)acetylene (2) initiated by ammonium persulfate/sodium formate ((NH4)2S2O8/HCO2Na) yield the addition-reduction product (3a), tribromide comp
- Qing, Feng-Ling,Wan, Dong-Peng
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p. 14189 - 14200
(2007/10/03)
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- α,α-Difluoroallyl carbanion: Indium-mediation in its facile coupling with aldehydes
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Indium-mediated coupling of aldehydes with 3-bromo-3,3-difluoropropene gives 1-substituted-2,2-difluorobut-3-en-1-ols in high yields at room temperature. The coupling takes place at the gem-difluorocarbon selectively. Ketones are inert under the condition
- Kirihara, Masayuki,Takuwa, Tomofumi,Takizawa, Shinobu,Momose, Takefumi
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p. 2853 - 2854
(2007/10/03)
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- Preparation of methylene-gem-difluorocyclopropanes and its reactivity as Michael Acceptor
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Preparation of methylene-gem-difluorocyclopropanes 3 was achieved through the selenoxide elimination reaction derived from gem- difluorocyclopropylmethanols 1, while this method can not be applied to non- fluorinated cyclopropylmethanols. The methylene-gem-difluorocyclopropane 3 showed a high reactivity as a Michael acceptor in the reaction with thiol or amine.
- Taguchi, Takeo,Kurishita, Masahito,Shibuya, Akira,Aso, Kifune
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p. 9497 - 9508
(2007/10/03)
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- Gem-Difluoroallylation of Aldehydes and Ketones as a Convenient Route to α,α-Difluorohomoallylic Alcohols
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In the presence of zinc, 3-bromo-3,3-difluoropropene or 3-iodo-1,1-difluoropropene reacted with carbonyl compounds to give the corresponding α,α-difluorohomoallylic alcohols in good yields at 0 deg C to room temperature.The reaction is applicable to aliph
- Yang, Zhen-Yu,Burton, Donald J.
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p. 1037 - 1041
(2007/10/02)
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- A facile preparation of gem-difluorohomoallylic alcohols[1]
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The reaction of 3-bromo-3,3-difluoropropene with zinc powder in THF at 0°C to room temperature in the presence of aldehydes and ketones provides a useful, easily scaled up route to gem-difluorohomoallylic alcohols. α,β-Unsaturated aldehydes and ketones gi
- Yang, Zhen-Yu,J. Burton, Donald
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p. 339 - 343
(2007/10/02)
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- Fluoride Ion-Catalyzed Generation and Carbonyl Addition of α-Halo Carbanions Derived from α-Halo Organosilicon Compounds
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The title carbanion species are generated from the corresponding α-haloorganosilicon compounds by the action of a catalytic amount of tris(diethylamino)sulfonium difluorotrimethylsilicate and are found to undergo addition to aldehyde carbonyl efficiently at ambient temperature.The synthetic potential of the reaction is demonstrated by application to the synthesis of some insecticides.
- Fujita, Makoto,Obayashi, Michio,Hiyama, Tamejiro
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p. 4135 - 4146
(2007/10/02)
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- PREPARATION AND CARBONYL ADDITION OF γ,γ-DIFLUOROALLYLSILANES
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The reaction of 3,3,3-trifluoropropenes with disilane/tetrabutylammonium fluoride or silyllithium reagent gives γ,γ-difluoroallylsilanes which afford gem-difluoroallyl adducts of aldehydes and ketones with the aid of a catalyst such as potassium t-butoxid
- Hiyama, Tamejiro,Obayashi, Michio,Sawahata, Miwa
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p. 4113 - 4116
(2007/10/02)
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- gem-(DIFLUOROALLYL)LITHIUM: PREPARATION BY LITHIUM-HALOGEN EXCHANGE AND UTILIZATION IN ORGANOSILICON AND ORGANIC SYNTHESIS.
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gem-(Difluoroallyl)lithium may be generated by lithium-bromine exchange between n-butyllithium and CH//2 equals CHCF//2Br at minus 95 degree C by using an in situ procedure. When this preparation is carried out in the presence of chlorosilanes, aldehydes, ketones, and esters, products are formed, often in good yield. The factors determining the regioselectivity in addition to C equals O of unsymmetrically substituted allylic lithium reagents are discussed.
- Seyferth,Simon,Sepelak,Klein
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p. 4634 - 4639
(2007/10/02)
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