- Preparation method and application of propyne aryl ether compound
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The invention particularly relates to a method for preparing propyne aryl ether compounds from aryl phenol, halogenated propyne and derivatives of the halogenated propyne, and belongs to the technical field of preparation of the propyne aryl ether compoun
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Paragraph 0069-0070
(2021/08/28)
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- Visible-Light-Induced Radical Carbo-Cyclization/ gem-Diborylation through Triplet Energy Transfer between a Gold Catalyst and Aryl Iodides
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Geminal diboronates have attracted significant attention because of their unique structures and reactivity. However, benzofuran-, indole-, and benzothiophene-based benzylic gem-diboronates, building blocks for biologically relevant compounds, are unknown. A promising protocol using visible light and aryl iodides for constructing valuable building blocks, including benzofuran-, indole-, and benzothiophene-based benzylic gem-diboronates, via radical carbo-cyclization/gem-diborylation of alkynes with a high functional group tolerance is presented. The utility of these gem-diboronates has been demonstrated by a 10 g scale conversion, by versatile transformations, by including the synthesis of approved drug scaffolds and two approved drugs, and even by polymer synthesis. The mechanistic investigation indicates that the merging of the dinuclear gold catalyst (photoexcitation by 315-400 nm UVA light) with Na2CO3 is directly responsible for photosensitization of aryl iodides (photoexcitation by 254 nm UV light) with blue LED light (410-490 nm, λmax = 465 nm) through an energy transfer (EnT) process, followed by homolytic cleavage of the C-I bond in the aryl iodide substrates.
- Hashmi, A. Stephen K.,Rominger, Frank,Si, Xiaojia,Zhang, Lumin
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supporting information
p. 10485 - 10493
(2020/07/03)
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- Iron-Mediated Cyclization of 1,3-Diynyl Propargyl Aryl Ethers with Dibutyl Diselenide: Synthesis of Selenophene-Fused Chromenes
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The synthesis of selenophene-fused chromene derivatives starting from 1,3-diynyl propargyl aryl ethers is reported herein. The method is based on carbon-carbon, carbon-selenium, selenium-carbon and carbon-selenium bonds formation in a one-pot protocol, using iron(III) chloride and dibutyl diselenide as promoters. The same reaction conditions were applied to propargyl anilines leading to the formation of 1-(butylselanyl)-selenophene quinolines. The results showed that the dilution and temperature of substrate addition had a crucial influence in the products obtained. When the substrates were added at room temperature, in the absence of a solvent, a mixture of products was obtained, whereas the slowly addition (15 min) of starting materials, as a dichloromethane solution, at 0 °C led to the product formation in good yields. The mechanistic study indicates that the cooperative action between iron(III) chloride and dibutyl diselenide was essential to promote the cyclization, whereas separately none of them was effective in promoting the cyclization. We proved the synthetic utility of heterocycles obtained in the Suzuki cross coupling reaction, giving the corresponding cross-coupled products in good yields. In addition, the organoselenium moiety was removed from the structures of products by using n-butyllithium. (Figure presented.).
- Back, Davi F.,Lutz, Guilherme,Zeni, Gilson
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p. 1096 - 1105
(2020/01/25)
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- Copper-Catalyzed Ring Opening of [1.1.1]Propellane with Alkynes: Synthesis of Exocyclic Allenic Cyclobutanes
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Despite the long history and interesting properties of propellanes, these compounds still have tremendous potential to be exploited in synthetic organic chemistry. Herein we disclose an experimentally simple procedure to achieve cyclobutane-containing allenes and alkynes through a copper-catalyzed ring opening of [1.1.1]propellane and subsequent reaction with ethynes.
- Lasányi, Dániel,Tolnai, Gergely L.
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supporting information
p. 10057 - 10062
(2019/12/24)
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- Waste-minimised copper-catalysed azide-alkyne cycloaddition in Polarclean as a reusable and safe reaction medium
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Herein we report the first example of a generally useful organic reaction, namely the copper-catalysed azide-alkyne cycloaddition, performed in a Polarclean/water mixture as a reaction medium. The process is very efficient, affording in 24 out of the 26 tested cases the desired triazole in quantitative yields. Product isolation is also very convenient, since the triazoles either precipitate or form a separate liquid phase, without the need to perform chromatographic separations. Moreover, since the metal catalyst is retained in the Polarclean/water phase, the catalyst/reaction medium can be easily reused for consecutive reaction runs, without an apparent loss in efficiency. This methodology is associated with very limited waste production, as evidenced by calculated E-factors in the range 2.6-3.7.
- Luciani, Lorenzo,Goff, Emily,Lanari, Daniela,Santoro, Stefano,Vaccaro, Luigi
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supporting information
p. 183 - 187
(2018/01/17)
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- Synthesis of Tricyclic Isoxazoles via Sequential [3+2] Dipolar Cycloaddition and Palladium-Catalyzed Intramolecular Arylation Reactions
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An efficient synthetic route to tricyclic isoxazoles via sequential copper-catalyzed 1,3-dipolar cycloaddition and palladium-catalyzed intramolecular arylation of isoxazoles is described. Based on these reactions, a convenient one-pot synthesis of the tri
- Guo, Dong-Cai,Zhang, Chao,Li, Fei,Zhang, Fenghua,Yu, Fang,He, Yu-Peng
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p. 1356 - 1370
(2017/03/11)
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- Palladium-Catalyzed Intramolecular Arylative Carboxylation of Allenes with CO2 for the Construction of 3-Substituted Indole-2-carboxylic Acids
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Arylative carboxylation of allenes proceeded in an intramolecular manner to afford the corresponding β,γ-unsaturated carboxylic acids in high yields using PdCl2/PAr3 (Ar = C6H4-p-CF3) and ZnEt2 under 1 atm of CO2. The intermediate of the cyclization/carboxylation sequence is thought to be a nucleophilic η1-allylethylpalladium, which reacts with CO2 at the γ-position of palladium. The products obtained could be efficiently converted into 3-substituted indole-2-carboxylate derivatives. One-pot synthesis of strychnocarpine, a β-carboline alkaloid, from the carboxylated product was also demonstrated.
- Higuchi, Yuki,Mita, Tsuyoshi,Sato, Yoshihiro
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supporting information
p. 2710 - 2713
(2017/05/24)
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- Palladium Catalyzed, Multicomponent Synthesis of Fused-Ring Pyrroles from Aryl Iodides, Carbon Monoxide, and Alkyne-Tethered Imines
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A palladium-catalyzed multicomponent route to polycyclic pyrroles is described. Pd(PtBu3)2 was found to catalyze the coupling of (hetero)aryl iodides, two equivalents of carbon monoxide and alkyne-tethered imines into 1,3-
- Firoozi, Neda,Torres, Gerardo M.,Arndtsen, Bruce A.
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supporting information
p. 11145 - 11152
(2016/11/28)
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- Intramolecular carbolithiation of heterosubstituted alkynes: An experimental and theoretical study
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A series of heterosubstitued alkynes was successfully submitted to the intramolecular carbolithiation of their triple bond. We show that the addition is stereoselective because of the control exerted by the terminal substituent X on the geometry of the transition state. A complementary DFT study suggests that the addition is anti when a strong Li-X interaction occurs.
- Lhermet, Rudy,Ahmad, Maha,Hauduc, Clémence,Fressigné, Catherine,Durandetti, Muriel,Maddaluno, Jacques
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supporting information
p. 8105 - 8111
(2015/05/27)
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- Synthesis of Potential Bioactive Novel 7-[2-Hydroxy-3-(1,2,3-triazol-1-yl) propyloxy]-3-alkyl-4-methylcoumarins
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A series of 50 novel 7-[2-hydroxy-3-(1,2,3-triazol-1-yl)propyloxy]-3-alkyl-4-methylcoumarins had been designed and synthesized in good to excellent yields via Cu(I)-catalyzed 1,3-dipolar cycloaddition reaction "click chemistry" of 7-(3-azido-2-hydroxypropyloxy)-3-alkyl-4-methylcoumarins with variety of acetylene derivatives. In turn, the precursor compound, that is, 7-(3-azido-2-hydroxypropyloxy)-3-alkyl-4-methylcoumarin, was synthesized by condensation of epichlorohydrin with 7-hydroxy-3-alkyl-4-methylcoumarins followed by opening of the epoxide ring in the resulted 7-epoxymethoxy-3-alkyl-4-methylcoumarins with sodium azide. All the synthesized compounds were unambiguously identified on the basis of their spectral data analyses (IR, 1H-NMR, 13C-NMR spectra, and HRMS).
- Arya, Anu,Kumar, Vinod,Mathur, Divya,Singh, Sukhdev,Brahma, Raju,Singh, Rajpal,Singh, Seema,Sharma,Parmar, Virinder S.,Prasad, Ashok K.
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- Cu(I)-catalyzed efficient synthesis of 2'-triazolo-nucleoside conjugates
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A small library of thirty-two 2'-triazolyl uridine and 2'-triazolyl-5-methyluridine has been synthesized by Cu(I)-catalyzed condensation of 2'-azido-2'-deoxyuridine and 2'-azido-2'-deoxy-5-methyluridine with different alkynes and aryl propargyl ethers in almost quantitative yields. Triazolo-nucleoside conjugates, which can be evaluated for different biological activity for suitable drug development, were unambiguously identified on the basis of 1H NMR, 13C NMR, IR, and HRMS data analysis. These compounds have been synthesized for the first time and have not been reported in the literature earlier.
- Mathur,Rana,Olsen,Parmar,Prasad
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p. 701 - 710
(2015/05/13)
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- Isopropanol and potassium tert-butoxide promoted intramolecular direct sp2 C-H functionalization: An expedient synthesis of 1,2,3-triazole annulated chromens and quinolones
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A series of 1,2,3-triazole annulated chromen and quinolone derivatives have been synthesized by means of direct sp2 C-H functionalization in the presence of iso-propanol and potassium tert-butoxide. The reaction proceeds through homolytic aroma
- Mondal, Biplab,Roy, Brindaban
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supporting information
p. 6123 - 6127
(2015/10/28)
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- Carbolithiation of chloro-substituted alkynes: A new access to vinyl carbenoids
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The intramolecular carbolithiation of a series of chloro-substituted alkynes leads to exocyclic alkylidene carbenoids of which both nucleophilic and electrophilic characters can be drove. A sole stereoselective 5-exo-dig addition takes place, probably bec
- Lhermet, Rudy,Ahmad, Maha,Fressigne, Catherine,Silvi, Bernard,Durandetti, Muriel,Maddaluno, Jacques
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supporting information
p. 10249 - 10254
(2014/08/18)
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- Facile construction of [6,6]-, [6,7]-, [6,8]-, and [6,9]ring-fused triazole frameworks by copper-catalyzed, tandem, one-pot, click and intramolecular arylation reactions: Elaboration to fused pentacyclic derivatives
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A sequential copper-catalyzed, one-pot, click reaction-intramolecular direct arylation, which involves two mechanistically distinct reactions (atom-economical click reaction and direct arylation of 1,2,3-triazole), to generate [6,6]-, [6,7]-, [6,8]-, and
- Nagarjuna Reddy,Kumara Swamy
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supporting information; experimental part
p. 2013 - 2022
(2012/05/05)
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- Synthetic applications of the nickel-catalyzed cyclization of alkynes combined with addition reactions in a domino process
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Carbonickelations of alkynes and functionalization of the resulting vinylnickel moiety have been performed efficiently in a nickel-catalyzed domino cyclization-condensation process. This reaction, which does not require the preparation of any other organometallic reagent, proceeds only by exo-dig cyclization. This convenient and mild method constitutes a one-pot synthesis of substituted dihydrobenzofurans, chromans, isochromans, indoles, or indanes. Theses valuable products are generally obtained in good yields and high stereoselectivity. They are shown to be useful synthons for rapid access to functionalized polycyclic skeletons. Yes nickel can! Carbonickelation of alkynes and functionalization of the resulting vinylnickel moiety occurs efficiently. Overall, a domino cyclization-condensation process propagated by substoichiometric nickel catalysis takes place (see scheme). This one-pot synthesis provides substituted polyheterocyclic compounds in good yields and high stereoselectivity.
- Durandetti, Muriel,Hardou, Lucie,Lhermet, Rudy,Rouen, Mathieu,Maddaluno, Jacques
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supporting information; experimental part
p. 12773 - 12783
(2011/12/04)
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- Synthesis and SAR of heterocyclic carboxylic acid isosteres based on 2-biarylethylimidazole as bombesin receptor subtype-3 (BRS-3) agonists for the treatment of obesity
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SAR around non-peptidic potent bombesin receptor subtype-3 (BRS-3) agonist lead 2 is presented. Attempts to replace the carboxylic acid with heterocyclic isosteres to improve oral bioavailability and brain penetration are described.
- Hadden, Mark,Goodman, Allan,Guo, Cheng,Guzzo, Peter R.,Henderson, Alan J.,Pattamana, Kevin,Ruenz, Megan,Sargent, Bruce J.,Swenson, Brian,Yet, Larry,Liu, Jian,He, Shuwen,Sebhat, Iyassu K.,Lin, Linus S.,Tamvakopoulos, Constantin,Peng, Qianping,Kan, Yanqing,Palyha, Oksana,Kelly, Theresa M.,Guan, Xiao-Ming,Metzger, Joseph M.,Reitman, Marc L.,Nargund, Ravi P.
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scheme or table
p. 2912 - 2915
(2010/07/02)
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- Identification of a boron-containing intermediate in the boron tribromide mediated aryl propargyl ether cleavage reaction
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An alternate reaction mechanism for the boron tribromide mediated deprotection of aryl propargyl ethers based on the isolation of a key boron-containing byproduct is proposed. On the basis of the new mechanistic insight, we discovered that HBBr2 · SMe2 can also be used for cleaving aryl propargyl ethers.
- Yao, Min-Liang,Reddy, Marepally Srinivasa,Zeng, Wenbin,Hall, Kelly,Walflsh, Ingrid,Kabalka, George W.
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supporting information; experimental part
p. 1385 - 1387
(2009/07/04)
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- Tributylgermanium hydride as a replacement for tributyltin hydride in radical reactions
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Tributylgermanium hydride (Bu3GeH) can be used as an alternative to tributyltin hydride (Bu3SnH) as a radical generating reagent with a wide range of radical substrates. Tributylgermanium hydride has several practical advantages over tributyltin hydride, e.g. low toxicity, good stability and much easier work-up of reactions. The reagent can be easily prepared in good yield and stored indefinitely. Suitable substrates include iodides, bromides, activated chlorides, phenyl selenides, tert-nitroalkanes, thiocarbonylimidazolides and Barton esters. Alkyl, vinyl and aryl radicals can be generated in radical reactions including reduction and cyclisation processes. Common radical initiators such as ACCN and triethylborane can be used. The slower rate of hydrogen abstraction by carbon-centred radicals from Bu 3GeH as compared to Bu3SnH facilitates improved cyclisation yields. Polarity reversal catalysis (PRC) with phenylthiol can be used in reactions which generate stable radical intermediates which will not abstract hydrogen from Bu3GeH.
- Bowman, W. Russell,Krintel, Sussie L.,Schilling, Mark B.
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p. 585 - 592
(2007/10/03)
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- Diastereoselective intramolecular SmI2-H2O-amine mediated couplings
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The effectiveness of SmI2-H2O-amine mixture for intramolecular couplings was discussed. Diastereoselectivities in the coupling of O-cyclohexanyliodophenol derivatives were provided into heterocycles. The amount of coupled product improved significantly as SmI2, the substrate and amine were premixed followed by a gradual addition of water.
- Dahlen, Anders,Petersson, Annika,Hilmersson, Goeran
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p. 2423 - 2426
(2007/10/03)
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- Palladium catalysed tandem cyclisation-anion capture processes. Part 3. Organoboron anion transfer agents
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The cyclisation-anion capture protocol has been applied to a wide range of starter and terminating species to effect regio- and stereo-specific mono- and bis-cyclisation processes in which a variety of organoboronderivatives function as anion transfer rea
- Grigg, Ronald,Sansano, Jose M.,Santhakumar, Vijayaratnam,Sridharan, Visuvanathar,Thangavelanthum, Ravishanker,Thornton-Pett, Mark,Wilson, David
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p. 11803 - 11826
(2007/10/03)
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- Chromium(II)-Mediated Nickel(II)-Catalysed Cyclisations of (Iodoaryl)-Substituted Alkynes and Alkynals
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The Chromium(II)-mediated Nickel(II)-catalysed cyclisations of (iodoaryl)-substituted alkynes 1, 2 and 7 and (iodoaryl)-substituted alkynals 9 and 10 to give the products 5, 6, 8, 11 and 12 respectively is described.
- Hodgson, David M.,Wells, Christopher
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p. 1601 - 1604
(2007/10/02)
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- Reductive Radical Cyclizations of Haloalkenes Promoted by Samarium Diiodide. Sequential Cyclization/Intermolecular Carbonyl Addition Reactions
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A sequential radical cyclization/intermolecular carbonyl addition process promoted by samarium(II) iodide (SmI2) is reported.Treatment of appropriate haloalkenes with SmI2 in the presence of a variety of ketones leads to products resulting from cyclization followed by intermolecular addition of the resultant anion to the carbonyl electrophiles.Although several mechanisms can be envisioned, this process is most likely initiated by SmI2-induced formation of a hexenyl radical.Intramolecular addition of this radical to the tethered alkene leads to generation of a new alkyl radical, which can be reduced in situ to the corresponding organosamarium species.This organosamarium adds to the carbonyl electrophile, completing the tandem process.In this study, 2-(allyloxy)ethyl iodide and 2-(allyloxy)-1-iodobenzene were the most thoroughly examined radical precursors.The anion intermediates ultimately derived from these starting materials were trapped with a range of ketones to yield the corresponding heterocyclic derivatives.
- Molander, Gary A.,Harring, Lori S.
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p. 6171 - 6176
(2007/10/02)
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- STEREOSELECTIVE SYNTHESIS OF (Z)-2,3-DIHYDRO-3-(ARYLMETHYLENE)BENZOFURANS VIA THE PALLADIUM CATALYSED INSERTION AND CROSS COUPLING REACTION OF 1-IODO-2-(2-PROPYNYLOXY)BENZENE AND ARYLZINC CHLORIDE
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The title compound was prepared in fair to good yields from 1-iodo-2-(2-propynyloxy)benzene and arylzinc chloride via tandem insertion and cross coupling reaction catalysed by pertinent palladium catalyst, such as palladium acetate and triphenylphosphine.
- Luo, Fen-Tair,Wang, Ren-Tzong
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p. 2181 - 2186
(2007/10/02)
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