- Ligand- and base-free synthesis of 1,3-diynes catalyzed by low loading of heterogeneous Pd/C and CuI
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A facile and environmentally friendly synthetic method for a variety of symmetrical 1,3-diyne derivatives based on the Pd/C-CuI-catalyzed homocoupling reaction of terminal alkynes has been developed. The reaction was efficiently catalyzed by the extremely
- Kurita, Takanori,Abe, Masami,Maegawa, Tomohiro,Monguchi, Yasunari,Sajiki, Hironao
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- Pd-catalysed cross coupling of terminal alkynes to diynes in the absence of a stoichiometic additive
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An efficient, room temperature procedure for the cross-coupling of a range of terminal alkynes, using standard Sonogashira cross-coupling conditions (Pd/Cu) is presented. At higher reaction temperatures, head-to-tail or head-to-head dimerisation affords 1,3- and 1,4-disubstituted enynes, respectively as minor products.
- Fairlamb, Ian J. S.,Baeuerlein, Patrick S.,Marrison, Lester R.,Dickinson, Julia M.
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- Synthesis of diynes by phase transfer catalysis in the presence of a Pd (0) catalyst
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A new method for diynes preparation by phase transfer catalysis in the presence of a Pd (0) catalyst is described.
- Vlassa,Ciocan-Tarta,Margineanu,Oprean
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- Polymer-Supported Cu–Nanoparticle as an Efficient and Recyclable Catalyst for Oxidative Homocoupling of Terminal Alkynes
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Abstract: Copper nanoparticle on polyaniline support was synthesised by using in situ polymerisation and composite formation technique. This metal polymer nanocomposites material is found to be efficient for homocoupling of terminal alkynes which afford s
- Aziz, Sk Tarik,Islam, Rafique Ul
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- CuI complexes with 2,2′-biquinolyl-containing polymeric ligands as electrocatalysts for the oxidative coupling of alkynes in the presence of dioxygen
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Electrocatalytic oxidative coupling of terminal alkynes in the presence of atmospheric oxygen catalyzed by CuI complexes with polymeric biquinolyl ligands leads to the corresponding diynes in high yield. The reaction proceeds under mild conditi
- Magdesieva,Dolganov,Yakimansky,Goikhman, M. Ya.,Podeshvo
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- Synthesis of symmetrical 1,3-diynes via homocoupling reaction of n-butyl alkynyltellurides
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An ultrasound-assisted synthesis of symmetrical 1,3-diyne compounds with electron-withdrawing or -donating substituents is described and illustrated by the palladium-catalyzed homocoupling reaction of n-butyl alkynyltellurides. This procedure offers easy
- Singh, Fateh V.,Amaral, M?nica F.Z.J.,Stefani, Hélio A.
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- Metallomicelle catalyzed aerobic tandem desilylation/Glaser reaction in water
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PEG-grafted nitrogen ligands were synthesized. The corresponding copper complexes serve as metallomicellar nanoreactors for the aerobic tandem desilylation/Glaser coupling of TMS-protected alkynes in water. The protocol is also suitable for base-free homocoupling of terminal alkynes. The metallomicellar catalyst could be recycled 5 times with minor loss of reactivity.
- Tang, Shanyu,Li, Longjia,Ren, Xuanhe,Li, Jiao,Yang, Guanyu,Li, Heng,Yuan, Bingxin
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supporting information
p. 2899 - 2904
(2019/06/17)
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- Chemoselective Cobalt(I)-Catalyzed Cyclotrimerization of (Un)Symmetrical 1,3-Butadiynes for the Synthesis of 1,2,4-Regioisomers
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The cobalt(I)-catalyzed cyclotrimerization of (un)symmetrical 1,4-disubstituted 1,3-butadiynes is presented. In the case of unsymmetrical 1,3-butadiynes, this reaction can generate eight 1,2,4-substituted and four 1,3,5-substituted isomers. A single 1,2,4-substituted isomer was formed in excellent yields (up to 99%) and exclusive regioselectivities (>99:1) when symmetrical or a 1,3-butadiyne with an aryl or alkyl substituent and a trimethylsilyl group were applied. A large number of products accepting a wide variety of functional groups were synthesized.
- Weber, Sebastian M.,Hilt, Gerhard
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supporting information
p. 4106 - 4110
(2019/06/17)
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- Synthesis of Aryl Alkynes via Copper Catalyzed Decarboxylative Alkynylation of 2-Nitrobenzoic Acids
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An efficient protocol for the synthesis of internal aryl alkynes was achieved via Cu-catalyzed decarboxylative cross-coupling reactions, and to the best of our knowledge, this is the first example of a Cu-catalyzed decarboxylative alkynylation of benzoic acids with terminal alkynes. This approach utilizes simple Cu salt as catalyst and O2, an abundant, clean, and green material, as the oxidant. The reaction tolerates various functional groups, and a variety of internal aryl alkynes were synthesized in 46-83% yields.
- Yu, Yongqi,Chen, Xiang,Wu, Qianlong,Liu, Da,Hu, Liang,Yu, Lin,Tan, Ze,Gui, Qingwen,Zhu, Gangguo
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supporting information
p. 8556 - 8566
(2018/06/29)
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- Continuous-flow oxidative homocouplings without auxiliary substances: Exploiting a solid base catalyst
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The catalytic oxidative dimerization of aromatic amines and acetylenes is of outstanding synthetic importance among homocoupling reactions. Both transformations necessitate the use of extraneous bases and ligands, which contains significant disadvantages as concerns environmental impacts and process costs. We exploited the inherent basic character of a copper-containing layered double hydroxide to facilitate the catalytic homocouplings of alkynes and aniline derivatives without the need for any auxiliary substances. The reactions were studied in a continuous-flow system to achieve extended parameter spaces for chemical intensification, and also to avoid undesired reaction pathways by means of strategic control over the residence time. Valuable 1,4-disubstituted 1,3-diynes and diversely substituted aromatic azo compounds were achieved chemoselectively in excellent yields and in short process times even on preparative scales.
- ?tv?s, Sándor B.,Georgiádes, ádám,Mészáros, Rebeka,Kis, Koppány,Pálinkó, István,Fül?p, Ferenc
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- Copper(i) chloride catalysed room temperature Csp-Csp homocoupling of terminal alkynes mediated by visible light
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We developed a technique mediated by visible light for the aerobic homocoupling of terminal alkynes to synthesize 1,3-conjugated diynes using a copper(i) chloride catalyst at room temperature. Compared with previously reported thermal processes, this photochemical method is simple, uses only mild reaction conditions, produces high yields and works well for substrates with electron-withdrawing groups without the need for bases/ligands, oxidants or palladium catalysts.
- Sagadevan, Arunachalam,Charpe, Vaibhav Pramod,Hwang, Kuo Chu
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p. 7688 - 7692
(2016/11/06)
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- 3,4-dihalo-2(5H)-furanones: A novel oxidant for the Glaser coupling reaction
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5-Alkoxy-3,4-dihalo-2(5H)-furanones could be used as a kind of novel oxidant in the Glaser coupling reaction. The screening of reaction conditions showed that both PdCl2(PPh3)2 and 3,4-dichloro-5-methoxy-2(5H)-furanone played crucial roles in the reaction. A possible reaction mechanism was proposed according to the reactivity of 3,4-dihalo-2(5H)-furanones. The new method easily allows the syntheses of alkyl and aryl substituted 1,3-diyne compounds. However, carbyne polymer was unexpectedly obtained when using trimethylsilyl acetylene as the substrate under the Glaser reaction condition.
- Li, Jian-Xiao,Liang, Hao-Ran,Wang, Zhao-Yang,Fu, Jian-Hua
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experimental part
p. 507 - 513
(2011/12/16)
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- Copper-zeolites as catalysts for the coupling of terminal alkynes: An efficient synthesis of diynes
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CuI-modified zeolites, especially CuI-USY, proved to be very efficient catalysts for the homocoupling of terminal alkynes. Such heterogeneous catalysts offer a very simple (no added ligand) and convenient synthesis of diynes, includi
- Kuhn, Philippe,Alix, Aurelien,Kumarraja, Mayilvasagam,Louis, Benoit,Pale, Patrick,Sommer, Jean
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experimental part
p. 423 - 429
(2009/06/18)
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- The behaviors of metal acetylides with dinitrogen tetroxide
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Lithium phenylacetylide (1a) and N2O4 (2) at - 78° yield diphenylbutadiyne (6a) by oxidative coupling, phenylacetylene (7a) by oxidation and then solvent H-abstraction, and benzoyl cyanide (8) by dimerizative-rearrangement of nitroso(phenyl)acetylene (23). Nitro(phenyl)acetylene (3, R = Ph) is not obtained. Benzonitrile (9), a further product, possibly results from hydrolytic decomposition of nitroso(phenyl)ketene (27) generated from phenylacetylenyl nitrite (26). Phenylacetylene (7a) and 2 give, along with (E)- and (Z)-1,2-dinitrostyrenes (34 and 35, resp.), 3-benzoyl-5-phenylisoxazole (10), presumably as formed by cycloaddition of benzoyl nitrile oxide (40) to 7a. Further, 2 reacts with other lithium acetylides (1b-1e), and with sodium, magnesium, zinc, copper, and copper lithium phenylacetylides, 1f-1l, to yield diacetylenes 6a-6c and monoacetylenes 7a-7c. Conversions of metallo acetylide aggregates to diacetylenes are proposed to involve generation and addition reactions of metallo acetylide radical cationic intermediates in cage, further oxidation, and total loss of metal ion. Loss of metal ions from metallo acetylide radical cations and H-abstraction by non-caged acetylenyl radicals will give terminal acetylenes. The principal reactions (75-100%) of heavy metal acetylides phenyl(trimethylstannyl)acetylene (44) and bis(phenylacetylenyl)mercury (47) with 2 are directed nitrosative additions (NO+) and loss of metal ions to give nitroso(phenyl)ketene (27), which converts to benzoyl cyanide (8).
- Woltermann, Christopher J.,Shechter, Harold
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p. 354 - 369
(2007/10/03)
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- Antimicrobial activity of polyacetylenes from Bellis perennis and their synthetic derivatives
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The chemical investigation of the essential oils from the aerial organs of Bellis perennis L., the common daisy, showed that polyacetylenes were one of the dominant class of compounds. The major constituents, methyl deca-4,6- diynoate and deca-4,6-diynoic acid, and their structural analogues, deca- 4,6-diyne, dimethyl octa-3,5-diyne-1,8-dioate and deca-4,6-diyne-1,10-dioic acid, were synthesised and their antimicrobial activity evaluated. Only deca- 4,6-diynoic acid and deca-4,6-diyne-1,10-dioic acid showed antimicrobial activity, being the two compounds mainly effective against Gram-positive and Gram-negative bacteria, respectively. Structure-activity relationships of the tested polyacetylenes are discussed.
- Avato, Pinarosa,Vitali, Cesare,Mongelli, Piernatale,Tava, Aldo
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p. 503 - 507
(2007/10/03)
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- Novel dienes and dienophiles, VII: Preparation and chemical behavior of 2,3-diethynyl-1,3-butadiene
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The two 2,3-diethynyl-1,3-butadiene derivatives 1b and 1c were prepared from 2,3-dichloro-1,3-butadiene (26) and the Grignard reagents 19b and 19c by Kumada coupling. Desilylation of 1b provided the parent molecule 1a. The title compounds were used for the preparation of numerous new enediyne systems by [2 + 4] cycloaddition. The dienophiles employed include maleic anhydride (27a), diethyl fumarate (29), tetracyanoethylene (31), diethyl azodicarboxylate (33), and dimethyl acetylenedicarboxylate (35). With p-quinones such as p-benzoquinone (44) as dienophiles the expected mono-and bisadducts are formed which were dehydrogenated to the bis- and tetrakis(trimethylsilylethynyl)naphtho- and -anthraquinones 47 and 48, respectively, by treatment with DDQ. Heating of 1b in THF at 65°C caused dimerization to the 1,5-cyclooctadiene derivative 56, which was desilylated to 1,2,5,6-tetraethynyl-1,5-cyclooctadiene (59) by treatment with potassium fluoride in DMF. 1b is approximately 15 times less reactive than 2,3-dimethyl-1,3-butadiene (54) towards maleic anhydride (27a). VCH Verlagsgesellschaft mbH, 1996.
- Hopf, Henning,Theurig, Marcus,Jones, Peter G.,Bubenitschek, Peter
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p. 1301 - 1311
(2007/10/03)
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- A procedure for the oxidative 'dimerization' of aliphatic 1-alkynes
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Aliphatic 1-alkynes RC≡CH (R = alkyl) are readily converted into diynes RC≡CC≡CR, by introducing oxygen into a mixture of the acetylene and pyridine using copper(I)bromide as a catalyst and 1,8-diazabicyclo[5.4.0] undec-7-ene as a co-catalyst.
- Brandsma,Verkruijsse,Walda
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p. 137 - 139
(2007/10/02)
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- A PALLADIUM-PROMOTED ROUTE TO 3-ALKYL-4-(1-ALKYNYL)-HEXA-1,5-DYN-3-ENES AND/OR 1,3-DYENES
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Reaction of benzene solutions of arylacetylenes with 1 equiv. of chloroacetone and 2 eqiuv. of Et3N, using a mixture of (PPh3)4Pd and CuJ as catalyst, affords 1,4-diaryl-butadiynes in very good yields.Under similar reaction conditions aliphatic 1-alkynes yield mixtures of simmetrically disubstituted 1,4-dialkyl-1,3-butadiynes and of 3-alkyl-4-(1-alkynyl)-hexa-1,5-diyn-3-enes.
- Rossi, Renzo,Carpita, Adriano,Bigelli, Clara
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p. 523 - 526
(2007/10/02)
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- Organocuprates as Electron Transfer Reagents. Evaluation for Conjugate Addition of Electrophiles to α,β-Unsaturated Ketones
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The reaction of a series of organocuprate containing alkyl, aryl, alkynyl, silylalkyl or phenylthio groups with (1) is reported.Some of these organocuprates showed electron transfer properties and were unreactive toward conjugate addition, hence have pote
- Hannah, Donald J.,Smith, Robin A.J.,Teoh, Irene,Weavers, Rex T.
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p. 181 - 188
(2007/10/02)
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- Stereospecific Synthesis of Conjugated Enynes from Alkenyldialkylboranes via Alkenylcopper Intermediates
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Alkenylcopper intermediates, readily generated from alkenylboron derivates of 9-borabicyclononane (9-BBN), undergo coupling with 1-halo-1-alkynes to provide stereodefined conjugated enynes of high isomeric purity and in yields approaching quantitative.
- Brown, Herbert C.,Molander, Gary A.
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p. 645 - 647
(2007/10/02)
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