- Design and synthesis of new 5-aryl-4-arylethynyl-1H-1,2,3-triazoles with valuable photophysical and biological properties
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Cu-catalyzed 1,3-dipolar cycloaddition of methyl 2-azidoacetate to iodobuta-1,3-diynes and subsequent Suzuki-Miyaura cross-coupling were used to synthesize new triazoles derivatives: 5aryl-4-arylethynyl-1H-1,2,3-triazoles. Investigation of their optical p
- Efremova, Mariia M.,Govdi, Anastasia I.,Frolova, Valeria V.,Rumyantsev, Andrey M.,Balova, Irina A.
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- In Situ Synthesis of CuN4/Mesoporous N-Doped Carbon for Selective Oxidative Crosscoupling of Terminal Alkynes under Mild Conditions
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The 1,3-conjugated diynes are an important class of chemical intermediates, and the selective crosscoupling of terminal alkynes is an efficient chemical process for manufacturing asymmetrical 1,3-conjugated diynes. However, it often occurs in homogenous conditions and costs a lot for reaction treatment. Herein, a copper catalyzed strategy is used to synthesize highly ordered mesoporous nitrogen-doped carbon material (OMNC), and the copper species is in situ transformed into the copper single-atom site with four nitrogen coordination (CuN4). These features make the CuN4/OMNC catalyst efficient for selective oxidative crosscoupling of terminal alkynes, and a wide range of asymmetrical and symmetrical 1,3-diynes (26 examples) under mild conditions (40?°C) and low substrates ratio (1.3). Density functional theory (DFT) calculations reveal that the aryl–alkyl crosscoupling has the lowest energy barrier on the CuN4 site, which can explain the high selectivity. In addition, the catalyst can be separated and reused by simply centrifugation or filtration. This work can open a facile avenue for constructing single-atom loaded mesoporous materials to bridge homogeneous and heterogeneous catalysis.
- Cao, Yue,Gu, Dong,Lei, Aiwen,Liang, Zhenjin,Su, Yaqiong,Wu, Jinsong,Wu, Yong,Xiao, Wei,Yang, Dali,Yu, Ruohan,Zhang, Dongchao,Zhang, Yuanteng
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- Tuning of cross-Glaser products mediated by substrate-catalyst polymeric backbone interactions
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Tuning of cross-Glaser products using different polymeric backbones supported by copper oxide nano-catalysts has been demonstrated by tweaking the substrate-catalyst interactions under greener conditions. Further, highly reactive magnetically separable and recyclable catalyst with scalability is demonstrated.
- Ali, Md. Ehesan,Dar, Arif Hassan,Gowri, Vijayendran,Jayamurugan, Govindasamy,Kaur, Sharanjeet,Mukhopadhyaya, Aritra,Neethu, K. M.,Sartaliya, Shaifali,Selim, Abdul
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supporting information
p. 2582 - 2585
(2020/03/10)
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- One-pot synthesis of unsymmetrical 1,3-butadiyne derivatives and their application in the synthesis of unsymmetrical 2,5-diarylthiophenes
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A one-pot protocol was developed for the synthesis of unsymmetrical 1,3-butadiynes. The procedure is based on two sequential reactions: deprotection of R–C≡C–C≡C– C(Me)2OH derivatives in a retro-Favorskii reaction to furnish a terminal 1,3-butadiyne compound, which reacted with aryl iod-ides in a Sonogashira-type cross-coupling reaction catalyzed by Pd(PPh3)4 and CuI, using TBAOH as activator and toluene as solvent under reflux for 10 min. We also studied in situ thiocycli-zation of 1,3-butadiynes, leading to unsymmetrical 2,5-diaryl-thiophenes. The principal features of this method are operational simplicity, good substrate scope, very fast reaction, and high yields.
- Andrade, Camila B.,Carvalho, Diego B.,Trefzger, Ozildéia S.,Kassab, Najla M.,Guerrero, Palimécio G.,Barbosa, Sandro L.,Shiguemoto, Cristiane Y. K.,Baroni, Adriano C. M.
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p. 696 - 704
(2019/01/04)
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- 1-Iodobuta-1,3-diynes in Copper-Catalyzed Azide-Alkyne Cycloaddition: A One-Step Route to 4-Ethynyl-5-iodo-1,2,3-triazoles
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Cu-catalyzed 1,3-dipolar cycloaddition of iododiacetylenes with organic azides using iodotris(triphenylphosphine)copper(I) as a catalyst was found to be an efficient one-step synthetic route to 5-iodo-4-ethynyltriazoles. The reaction is tolerant to various functional groups in both butadiyne and azide moieties. The synthetic application of 5-iodo-4-ethynyl triazoles obtained was also evaluated: the Sonogashira coupling with alkynes resulted in unsymmetrically substituted triazole-fused enediyne systems, while the Suzuki reaction yielded the corresponding 5-aryl-4-ethynyl triazoles.
- Govdi, Anastasia I.,Danilkina, Natalia A.,Ponomarev, Alexander V.,Balova, Irina A.
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- Copper Nanoparticles on Ordered Mesoporous Carbon Nitride Support: a Superior Catalyst for Homo- and Cross-Coupling of Terminal Alkynes under Base-Free Conditions
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A novel ordered mesoporous carbon nitride (OMCN) was synthesized as a functionalized support with 2,4,6-trichloro-1,3,5-triazine and benzidine as starting materials in the presence of SBA-15 as a template. Copper nanoparticles were then loaded on the C–N material to achieve a novel nanocomposite catalyst (Cu NPs-OMCN). The nanocomposite was utilized as a highly efficient catalyst for homo- and cross-coupling of terminal alkynes under base-free conditions in ethanol, and various symmetrical and unsymmetrical 1,3-diynes were obtained with good to excellent yields. Moreover, based on this reaction, a one-pot approach to synthesize 2,5-disubstituted thiophenes and furans from terminal alkynes were developed. Furthermore, the heterogeneous catalyst could be recovered and reused conveniently for several times with satisfactory yields.
- Xu, Hang,Wu, Liangying,Tian, Jing,Wang, Jun,Wang, Peng,Niu, Xiyu,Yao, Xiaoquan
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p. 6690 - 6696
(2019/11/02)
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- Transition-Metal-Free Synthesis of Borylated Thiophenes via Formal Thioboration
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A simple, regiocontrolled, and transition-metal-free approach to access exclusively 3-borylated thiophene derivatives is reported. The commercially available B-chlorocatecholborane reagent (ClBcat) acts as a carbophilic Lewis acid to activate the alkyne i
- Bel Abed, Hassen,Blum, Suzanne A.
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supporting information
p. 6673 - 6677
(2018/10/24)
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- Copper Catalysis for Selective Heterocoupling of Terminal Alkynes
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A Cu-catalyzed selective aerobic heterocoupling of terminal alkynes is disclosed, which enables the synthesis of a broad range of unsymmetrical 1,3-diynes in good to excellent yields. The results disprove the long-held belief that homocouplings are exclusively favored in the Glaser-Hay reaction.
- Su, Lebin,Dong, Jianyu,Liu, Long,Sun, Mengli,Qiu, Renhua,Zhou, Yongbo,Yin, Shuang-Feng
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supporting information
p. 12348 - 12351
(2016/10/07)
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- Application of organoselenides in the Suzuki, Negishi, Sonogashira and Kumada cross-coupling reactions
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We reported herein the regio- and stereoselective palladium-catalyzed cross-coupling reactions of unsaturated organoselenides with Sonogashira, Suzuki, Negishi and Kumada partners. The reactions were in general carried out with Pd(PPh3)4 (10 mol%), in DMF at 80 °C to afford the cross-coupling products in good yields. This strategy tolerated a wide range of substrates, such as alkynyl, vinyl, aryl and heteroaryl selenides with a variety of sensitive functional groups and gave the cross-coupling products in good yields.
- Stein,Bilheri,Zeni
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supporting information
p. 15522 - 15525
(2015/10/28)
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- Copper-catalyzed three-component synthesis of 3-Aminopyrazoles and 4-iminopyrimidines via β-alkynyl-N-sulfonyl ketenimine intermediates
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3-Aminopyrazoles and 4-iminopyrimidines were efficiently prepared via copper-catalyzed three-component reactions of butadiynes, sulfonylazides, and hydrazides or imidamides. The reactions were regioselectively approached via the formation of a β-alkynyl-N-sulfonyl ketenimine intermediate which represented a new and effective 1,3-dielectrophilic equivalent in organic synthesis.
- Xing, Yanpeng,Cheng, Binyu,Wang, Jing,Lu, Ping,Wang, Yanguang
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p. 4814 - 4817
(2015/04/27)
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- Trisulfur radical anion as the key intermediate for the synthesis of thiophene via the interaction between elemental sulfur and NaO t Bu
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A facile base-promoted sulfur-centered radical generation mode and a single-step protocol for the synthesis of thiophene derivatives using 1,3-diynes via the interaction between elemental sulfur and NaOtBu has been reported. EPR experiments revealed that the trisulfur radical anion acts as a key intermediate of this process. A plausible mechanism has been proposed.
- Zhang, Guoting,Yi, Hong,Chen, Hong,Bian, Changliang,Liu, Chao,Lei, Aiwen
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supporting information
p. 6156 - 6159
(2015/01/16)
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- Rational design of a palladium-catalyzed Csp-Csp cross-coupling reaction inspired by kinetic studies
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Less is More: A highly selective Pd-catalyzed Csp-Csp cross-coupling reaction between terminal alkynes and 1-bromoacetylenes has been developed. Catalyst loading is low (only 0.0001-0.01 mol % of Pd is required) and provides products with high selectivities and good to excellent yields under mild conditions. TBAB=tetrabutylammonium bromide, TON=turnover number. Copyright
- Weng, Yue,Cheng, Ben,He, Chuan,Lei, Aiwen
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supporting information
p. 9547 - 9551
(2012/10/30)
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- Zinc-mediated enantioselective addition of terminal 1,3-diynes to N-arylimines of trifluoropyruvates
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A facile and effective enantioselective addition of terminal 1,3-diynes to acyclic α-CF3 ketimine esters has been developed by using zinc/Binol complexes. The reaction works well with a variety of aromatic-, aliphatic- and silyl-substituted diynes, providing the desired products in up to 97% yield and 97% enantiomeric excess.
- Zhang, Fa-Guang,Ma, Hai,Zheng, Yan,Ma, Jun-An
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scheme or table
p. 7663 - 7669
(2012/09/05)
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- An approach to organic ferromagnets. Synthesis and characterization of 1-phenyl-1,3-butadiyne polymers having a persistent nitroxide group on the phenyl ring
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1-[3-(N-tert-Butylhydroxyamino)-4-chlorophenyl]-1,3-butadiyne (3) was obtained as colorless needles (mp ca. 140 °C from diethyl ether) that polymerized 100% in 24 h at 120°C to give a black, ethanol-insoluble microcrystalline product. Crystals of 3 are tr
- Inoue, Katsuya,Koga, Noboru,Iwamura, Hiizu
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p. 9803 - 9810
(2007/10/02)
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