- A Unified Strategy for the Synthesis of Difluoromethyl- And Vinylfluoride-Containing Scaffolds
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Here, we report a general method for the synthesis of quaternary and tertiary difluoromethylated compounds and their vinylfluoride analogues. The strategy, which relies on a two-step sequence featuring a C-selective electrophilic difluoromethylation and either a palladium-catalyzed decarboxylative protonation or a Krapcho decarboxylation, is practical, scalable, and high yielding. Considering the generality of the method and the attractive properties offered by the difluoromethyl group, this approach provides a valuable tool for late-stage functionalization and drug development.
- Duchemin, Nicolas,Buccafusca, Roberto,Daumas, Marc,Ferey, Vincent,Arseniyadis, Stellios
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supporting information
p. 8205 - 8210
(2019/10/16)
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- Highly Enantioselective, Base-Free Synthesis of α-Quaternary Succinimides through Catalytic Asymmetric Allylic Alkylation
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The synthesis of diversely substituted five-membered ring succinimide derivatives is reported featuring a direct, base-free, palladium-catalyzed asymmetric allylic alkylation. The method allows a straightforward access to the desired heterocyclic scaffold bearing an all-carbon α-quaternary stereogenic center in high yields and good to excellent enantioselectivities. To further demonstrate the synthetic utility of the method, the allylated products were further converted to various versatile chiral building blocks, including a chiral pyrrolidine and a spirocyclic derivative, using selective transformations.
- Song, Tao,Arseniyadis, Stellios,Cossy, Janine
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supporting information
p. 8076 - 8080
(2018/06/15)
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- Tri(pentaflurophenyl)borane-catalyzed reduction of cyclic imides with hydrosilanes: Synthesis of pyrrolidines
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B(C6F5)3-catalyzed hydrosilylation of cyclic imides afforded an efficient synthetic method of pyrrolidines. In the presence of 5 mol% B(C6F5)3, various aromatic, aliphatic and polycyclic imides were smoothly reduced by PhSiH3 to generate the corresponding pyrrolidines in high yields. The reaction profiles monitored by 1H NMR spectroscopy disclosed the reduction process of cyclic imides and the effect of difference structure of the hydrosilanes on the hydrosilylation.
- Ding, Guangni,Wu, Xiaoyu,Lu, Bin,Lu, Wenkui,Zhang, Zhaoguo,Xie, Xiaomin
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supporting information
p. 1144 - 1150
(2018/02/17)
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- Synthesis of Cyclic Imides by Acceptorless Dehydrogenative Coupling of Diols and Amines Catalyzed by a Manganese Pincer Complex
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The first example of base-metal-catalyzed dehydrogenative coupling of diols and amines to form cyclic imides is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese and forms hydrogen gas as the sole byproduct, making the overall process atom economical and environmentally benign.
- Espinosa-Jalapa, Noel Angel,Kumar, Amit,Leitus, Gregory,Diskin-Posner, Yael,Milstein, David
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supporting information
p. 11722 - 11725
(2017/09/07)
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- MANGANESE BASED COMPLEXES AND USES THEREOF FOR HOMOGENEOUS CATALYSIS
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The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di- lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.
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Paragraph 00396
(2017/09/05)
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- Antiproliferative and antibacterial activity of some glutarimide derivatives
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Antiproliferative and antibacterial activities of nine glutarimide derivatives (1–9) were reported. Cytotoxicity of compounds was tested toward three human cancer cell lines, HeLa, K562 and MDA-MB-453 by MTT assay. Compound 7 (2-benzyl-2-azaspiro[5.11]heptadecane-1,3,7-trione), containing 12-membered ketone ring, was found to be the most potent toward all tested cell lines (IC50 = 9–27 μM). Preliminary screening of antibacterial activity by a disk diffusion method showed that Gram-positive bacteria were more susceptible to the tested compounds than Gram-negative bacteria. Minimum inhibitory concentration (MIC) determined by a broth microdilution method confirmed that compounds 1, 2, 4, 6–8 and 9 inhibited the growth of all tested Gram-positive and some of the Gram-negative bacteria. The best antibacterial potential was achieved with compound 9 (ethyl 4-(1-benzyl-2,6-dioxopiperidin-3-yl)butanoate) against Bacillus cereus (MIC 0.625 mg/mL; 1.97 × 10?3mol/L). Distinction between more and less active/inactive compounds was assessed from the pharmacophoric patterns obtained by molecular interaction fields.
- Popovi?-Djordjevi?, Jelena B.,Klaus, Anita S.,?i?ak, ?eljko S.,Mati?, Ivana Z.,Drakuli?, Branko J.
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p. 915 - 923
(2016/10/09)
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- Radical-mediated dehydrative preparation of cyclic imides using (NH4)2S2O8-DMSO: Application to the synthesis of vernakalant
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Ammonium persulfate-dimethyl sulfoxide (APS-DMSO) has been developed as an efficient and new dehydrating reagent for a convenient one-pot process for the synthesis of miscellaneous cyclic imides in high yields starting from readily available primary amines and cyclic anhydrides. A plausible radical mechanism involving DMSO has been proposed. The application of this facile one-pot imide forming process has been demonstrated for a practical synthesis of vernakalant.
- Garad, Dnyaneshwar N.,Tanpure, Subhash D.,Mhaske, Santosh B.
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p. 1008 - 1016
(2015/08/18)
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- PROCESS OF FORMING A CYCLIC IMIDE
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A process is provided for the synthesis of a cyclic imide. A primary amine and a diol compound are contacted in the presence of a Ruthenium (II) complex. The Ruthenium (II) catalyst includes at least one of an alicyclic ligand, an aromatic ligand, an arylalicyclic ligand, an arylaliphatic ligand and a phosphine ligand.
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Page/Page column 34
(2012/01/15)
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- Dehydrogenative amide synthesis: Azide as a nitrogen source
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A new atom-economical strategy to amide linkage from an azide and alcohol liberating hydrogen and nitrogen was developed with an in situ generated ruthenium catalytic system. The reaction has broad substrate generality including diols for the synthesis of cyclic imides.
- Fu, Zhenqian,Lee, Jeongbin,Kang, Byungjoon,Hong, Soon Hyeok
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supporting information
p. 6028 - 6031
(2013/02/22)
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- Synthesis and asymmetric hydrogenation of (3E)-1-benzyl-3-[(2-oxopyridin- 1(2H)-yl)methylidene]piperidine-2,6-dione
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The synthesis of (3E)-1-benzyl-3-[(2-oxopyridin-1(2H)-yl)methylidene] piperidine-2,6-dione 4 from N-benzylglutarimide was achieved in three steps. The asymmetric hydrogenation of 4 gave either the product of partial reduction (10) or full reduction (13), depending on the catalyst which was employed, in high ee in each case. Attempts at asymmetric transfer hydrogenation (ATH) of 4 resulted in formation of a racemic product. The Royal Society of Chemistry.
- Bisset, Alexander A.,Shiibashi, Akira,Desmond, Jasmine L.,Dishington, Allan,Jones, Teyrnon,Clarkson, Guy J.,Ikariya, Takao,Wills, Martin
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p. 11978 - 11980
(2013/01/16)
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- Synthesis of 2-azabicyclo[4.1.0]heptanes through stereoselective cyclopropanation reactions
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Unsaturated δ-lactams are cyclopropanated with the aid of diazo compound decomposition catalysed by metal complexes. A study of the reaction conditions, stereochemical outcome and group protection is reported. The resulting bicyclic products are related to bioactive compounds. Transformation into thiolactams facilitates the separation of the different isomers obtained and the removal of the protecting group. The cyclopropanation reaction works with diverse diazo compounds. Unsaturated δ-lactams are cyclopropanated with the aid of diazo compound decomposition catalysed by metal complexes. A study of the reaction conditions, stereochemical outcome and group protection isreported. Transformation into thiolactams assists in separation of the different isomers obtained and removal of the protecting group.
- Suarez Del Villar, Irene,Gradillas, Ana,Perez-Castells, Javier
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experimental part
p. 5850 - 5862
(2011/03/17)
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- Synthesis of cyclic imides from simple diols
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There's something imide so strong: Cyclic imides were synthesized from simple diols with primary amines in a single step using an in-situ-generated ruthenium catalytic system. The atom-economical and operatively simple syntheses of succinimides, phthalimides, and glutarimides, which are important building blocks in natural products and drugs, was also demonstrated. Copyright
- Zhang, Jian,Senthilkumar, Muthaiah,Ghosh, Subhash Chandra,Hong, Soon Hyeok
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supporting information; experimental part
p. 6391 - 6395
(2010/11/05)
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- An efficient protocol for the synthesis of N-Alkyl- and N-Arylimides using the lewis acidic ionic liquid choline chloride-2ZnCl2
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Lewis acidic ionic liquid choline chloride-2ZnCl2 is shown to be for the first time an excellentmedium and efficient catalyst for the synthesis of N-alkyl- and N-arylimides in good yields under mild conditions.
- Xiea, You-Teng,Houb, Rei-Sheu,Wangb, Huey-Min,Kangc, Iou-Jiun,Chena, Ling-Ching
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experimental part
p. 839 - 842
(2010/08/13)
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- Titanium- And Lewis acid-mediated cyclopropanation of imides
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We report a straightforward synthesis of 1-azaspirocyclopropane lactams from imides. Following the described procedure, polycyclic nitrogen heterocycles containing a cyclopropane unit could be obtained from unsaturated imides.
- Bertus, Philippe,Szymoniak, Jan
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p. 659 - 662
(2008/02/05)
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- Chemoselective hydrogenation of imides catalyzed by Cp*Ru(PN) complexes and its application to the asymmetric synthesis of paroxetine
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This work represents the first catalytic hydrogenation of imides into amides and primary alcohols, in which the unique chemoselectivity is originated from the bifunctional nature of ruthenium-NH moiety in the catalyst. Copyright
- Ito, Masato,Sakaguchi, Ayaka,Kobayashi, Chika,Ikariya, Takao
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p. 290 - 291
(2008/04/18)
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- Concise and short synthesis of functionalized 5,6-dihydropyridin-2-ones by means of palladium(0)-catalyzed cross-coupling of ketene aminal phosphates
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A concise and short synthetic entry to 5,6-dihydropyridin-2-one derivatives has been developed by means of palladium(0)-catalyzed cross-coupling of cyclic ketene aminal phosphates.
- Fuwa, Haruhiko,Kaneko, Akane,Sugimoto, Yasuaki,Tomita, Taisuke,Iwatsubo, Takeshi,Sasaki, Makoto
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p. 101 - 106
(2007/10/03)
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- Diisopropyloxy(η2-cyclopentene)titanium for the diastereoselective synthesis of various 1,2-disubstituted cyclopentanes
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The reaction of 3 equiv of cyclopentylmagnesium chloride with 2 equiv of titanium(IV) isopropoxide at low temperature (-70 to -50 °C) leads to the formation of 1 equiv of diisopropyloxy(η2-cyclopentene)titanium containing low amounts of the starting Grignard reagent. The sequential addition of two electrophiles onto this titanium complex involved as an intermediate in Kulinkovich-type reactions delivers various 1,2-disubstituted cyclopentane rings with generally high diastereoselectivity. Mechanistic considerations and possible extensions of this method are discussed.
- Cadoret, Frédéric,Retailleau, Pascal,Six, Yvan
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p. 7749 - 7753
(2007/10/03)
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- Solvent free N-alkyl and N-arylimides preparation from anhydrides catalyzed by TaCl5-silica gel
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The first Lewis acid catalyzed and solvent free procedure for the preparation of imides from the corresponding anhydrides is described involving TaCl5-silica gel as Lewis acid under microwave irradiation.
- Chandrasekhar,Takhi, Mohamed,Uma
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p. 8089 - 8092
(2007/10/03)
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- REACTIVITY OF IMINOPHOSPHORANES TOWARDS SOME SYMMETRICAL DICARBONYL DICHLORIDES : SYNTHESES AND MECHANISMS
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In situ generated iminophosphoranes 1 react with dicarbonyl dihalides 2a-b and 3a-c to give known or new nitrogen heterocycles.The proposed mechanisms involve elimination of either triphenyl-phosphine oxide or dichlorotriphenylphosphorane depending upon both the iminophosphorane and the dicarbonyl compound.
- Aubert, Thierry,Farnier, Michel,Guilard, Roger
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- A SYNTHESIS OF SUCCINIMIDES AND GLUTARIMIDES FROM CYCLIC ANHYDRIDES
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The transformation of cyclic anhydrides to their corresponding imides involves a mild three-step sequence: (1) reaction with a primary amine, (2) conversion of the intermadiate monoamide to an N-hydroxysuccinimidyl ester using N,N'-disuccinimidyl oxalate
- Kometani, Tadashi,Fitz, Tony,Watt, David S.
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p. 919 - 922
(2007/10/02)
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