- AgOTf-catalyzed electrophilic cyclization of triynols with NXS: Rapid synthesis of densely trisubstituted naphthalenes and quinolines
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A silver triflate-catalyzed electrophilic cyclization reaction of acyclic triynols with NXS (X=I, Br) under mild conditions is reported. Three reactive functional groups, such as a carbonyl group, an alkyne group, and a halogen, could be selectively installed at the C1, C2, and C3 positions to obtain the naphthalene and quinoline products, respectively. The obtained densely trisubstituted products could be further transformed into more complex aromatic products by manipulating the alkynyl moiety and the other two functional groups as synthons. Copyright
- Chen, Zhiyuan,Jia, Xuegong,Ye, Changqing,Qiu, Guanyinsheng,Wu, Jie
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Read Online
- Synthesis of (Z)-1-phenylseleno-1,4-diorganyl-1-buten-3-ynes: Hydroselenation of symmetrical and unsymmetrical 1,4-diorganyl-1,3-butadiynes
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The hydroselenation of 1-organyl-1,3-butadiynes and 1,4-diorganyl-1,3-butadiynes with the sodium phenylselenolate anion, which was generated in situ by reacting diphenyl diselenide with NaBH4 in aqueous ethanol, results in the regio-, stereo- and chemoselective formation the 1-phenylseleno-4-organyl-1-buten-3-ynes and 1-phenylseleno-1,4-diorganyl-1-buten-3-ynes of Z configuration respectively. The lack of selectivity with the 2-hydroxy-2-methyl-3,5-dodecadiyne was observed and the obtained product structures were studied in detail.
- Dabdoub, Miguel J.,Baroni, Adriano C.M.,Lenard?o, Eder J.,Gianeti, Thiago R.,Hurtado, Gabriela R.
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Read Online
- 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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- A new type of carborane-based electron-accepting material
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In this study, a new type of carborane-based electron acceptor was prepared by the direct attachment of an ethynyl group to the carboranyl carbon atom. Analyses of photophysical and electrochemical and DFT calculations suggested that the direct attachment of the ethynl group significantly affects the electrochemical properties of these o-carborane systems. This journal is
- Lee, Sunhee,Shin, Jisu,Ko, Doo-Hyun,Han, Won-Sik
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supporting information
p. 12741 - 12744
(2020/11/02)
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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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- Rh(III)-Catalyzed [3 + 2] Spirocyclization of 2 H-Imidazoles with 1,3-Diynes for the Synthesis of Spiro-[imidazole-indene] Derivatives
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An effective strategy to synthesize spirocyclic compounds, [imidazole-4,1′-indene], has been efficaciously developed relied on Rh(III)-catalyzed [3 + 2] spirocyclization of 2H-imidazoles and 1,3-diynes with excellent chemselectivity and regioselectivity.
- Luo, Yi,Liu, Hao,Zhang, Jing,Liu, Man,Dong, Lin
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supporting information
p. 7604 - 7608
(2020/10/09)
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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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- 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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- 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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- An efficient heterogeneous palladium(0)-catalysed cross-coupling between 1-bromoalkynes and terminal alkynes leading to unsymmetrical 1,3-diynes
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An efficient heterogeneous palladium(0)-catalysed cross-coupling of 1-bromoalkynes with terminal alkynes was achieved in DMF at room temperature in the presence of 5 mol% of MCM-41-immobilised bidentate phosphine palladium(0) complex [MCM-41-2P-Pd(0)] and 2 mol% of CuI with Et3N as base, yielding a variety of unsymmetrical 1,3-diynes in moderate to good yields. This heterogeneous palladium(0) complex could be easily recovered by a simple filtration of the reaction solution and recycled at least seven times without significant decrease in activity.
- Xu, Zhaotao,Ai, Jinting,Cai, Mingzhong
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p. 133 - 137
(2018/04/20)
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- Alkyne compound and synthesis method and application thereof
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The invention relates to the field of organic synthesis, in particular to an alkyne compound and a synthesis method and application thereof. The invention discloses a method for synthesizing an alkynecompound, which comprises the following steps: allowing a compound in formula (II) and a compound in formula (III) to react in the presence of an inert solvent under the action of catalyst and oxidizing agent to obtain a compound in formula (I). The synthesis method has simple and easily available materials, safe and simple operation, wide application range of substrate and good selectivity, doesn't need pre-activating, and is easily involved in free radical reaction, and byproducts are nitrogen and water, which conforms to sustainable green chemistry. The alkyne compound obtained by the above synthesis method is a brand-new alkyne compound, and the alkyne compound can be widely used in the fields of medicine and materials, and solves the technical problems of high cost, low stability andcomplication of alkyne compound synthesis reaction in the prior art.
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Paragraph 0097-0099
(2018/12/13)
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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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- Selective Hydroarylation of 1,3-Diynes Using a Dimeric Manganese Catalyst: Modular Synthesis of Z-Enynes
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The transition-metal-catalyzed selective hydroarylation of unsymmetrical alkynes represents the state-of-art in organic chemistry, and still mainly relies on the use of precious late-transition-metal catalysts. Reported herein is an unprecedented MnI-catalyzed hydroarylation of unsymmetrical 1,3-diyne alcohols with commercially available arylboronic acids with predictive selectivity. This method addresses the challenges in regio-, stereo-, and chemoselectivity. It offers a general, convenient and practical strategy for the modular synthesis of multisubstituted Z-configurated conjugated enynes. This protocol is distinguished by its operational simplicity, complete selectivity, excellent functional-group compatibility, and gram-scale potential. A dimeric MnI species, Mn2(CO)8Br2, was proven to be a much more efficient catalyst precursor than Mn(CO)5Br.
- Yan, Zhongfei,Yuan, Xiang-Ai,Zhao, Yue,Zhu, Chengjian,Xie, Jin
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supporting information
p. 12906 - 12910
(2018/09/25)
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- Cyclobutene vs 1,3-Diene Formation in the Gold-Catalyzed Reaction of Alkynes with Alkenes: The Complete Mechanistic Picture
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The intermolecular gold(I)-catalyzed reaction between arylalkynes and alkenes leads to cyclobutenes by a [2 + 2] cycloaddition, which takes place stepwise, first by formation of cyclopropyl gold(I) carbenes, followed by a ring expansion. However, 1,3-butadienes are also formed in the case of ortho-substituted arylalkynes by a metathesis-type process. The corresponding reaction of alkenes with aryl-1,3-butadiynes, ethynylogous to arylalkynes, leads exclusively to cyclobutenes. A comprehensive mechanism for the gold(I)-catalyzed reaction of alkynes with alkenes is proposed on the basis of density functional theory calculations, which shows that the two pathways leading to cyclobutenes or dienes are very close in energy. The key intermediates are cyclopropyl gold(I) carbenes, which have been independently generated by retro-Buchner reaction from stereodefined 1a,7b-dihydro-1H-cyclopropa[a]naphthalenes.
- De Orbe, M. Elena,Amenós, Laura,Kirillova, Mariia S.,Wang, Yahui,López-Carrillo, Verónica,Maseras, Feliu,Echavarren, Antonio M.
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supporting information
p. 10302 - 10311
(2017/08/09)
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- Gold-Catalyzed Cadiot–Chodkiewicz-type Cross-Coupling of Terminal Alkynes with Alkynyl Hypervalent Iodine Reagents: Highly Selective Synthesis of Unsymmetrical 1,3-Diynes
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A new and efficient method for the synthesis of unsymmetrical 1,3-butadiynes by gold-catalyzed C(sp)–C(sp) cross-coupling of terminal alkynes with alkynyl hypervalent iodine(III) reagents has been developed. The reaction features high selectivity and efficiency, mild reaction conditions, wide substrate scope, and functional-group compatibility, and is a highly attractive complement to existing methods. Mechanistic studies reveal that formation of a phenanthrolinyl-ligated gold(I) complex is crucial for the efficiency and selectivity of the target transformation.
- Li, Xiangdong,Xie, Xin,Sun, Ning,Liu, Yuanhong
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supporting information
p. 6994 - 6998
(2017/06/08)
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- Glaser-Hay hetero-coupling in a bimetallic regime: A Ni(II)/Ag(i) assisted base, ligand and additive free route to selective unsymmetrical 1,3-diynes
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A Ni(OAc)2/Ag(OTf) catalysed coupling of aryl alkynes and propargylic alcohol/ether/ester gave the corresponding unsymmetrical 1,3-diynes in good to excellent yields. The reaction does not require bases, ligands or additives and shows excellent hetero-selectivity, thereby addressing the current challenges in the field of coupling of two different terminal alkynes.
- Mohanty, Anuradha,Roy, Sujit
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supporting information
p. 10796 - 10799
(2017/10/06)
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- Computer-Assisted Design of Ionic Liquids for Efficient Synthesis of 3(2H)-Furanones: A Domino Reaction Triggered by CO2
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A strategy for the highly efficient synthesis of 3(2H)-furanones by hydration of diyne alcohols catalyzed by base-functionalized ionic liquids under atmospheric-pressure CO2 that was developed through computer-assisted design is reported. The best range of basic ionic liquids as catalysts was predicted at first, and [HDBU][BenIm] exhibited the highest catalytic activity. Through a combination of NMR spectroscopic investigations and quantum-chemical calculations, the results indicated the importance of the basicity of the anion and the species of cation in the ionic liquid.
- Chen, Kaihong,Shi, Guiling,Zhang, Weidong,Li, Haoran,Wang, Congmin
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supporting information
p. 14198 - 14201
(2016/11/13)
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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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- Visible-light-activated copper(i) catalyzed oxidative Csp-Csp cross-coupling reaction: Efficient synthesis of unsymmetrical conjugated diynes without ligands and base
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A novel visible-light-promoted copper-catalysed process for the Csp-Csp cross-coupling reaction of terminal alkynes at room temperature is described. The current photochemical method is simple, highly functional group compatible, and more viable towards the construction of bio-active 1,3-unsymmetrical conjugated diynes without the need of bases/ligands, additives and expensive palladium/gold catalysts.
- Sagadevan, Arunachalam,Lyu, Ping-Chiang,Hwang, Kuo Chu
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supporting information
p. 4526 - 4530
(2016/08/18)
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- Silver-catalyzed synthesis of 1-chloroalkynes directly from terminal alkynes
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An efficient method to prepare 1-chloroalkynes was investigated. The method involved the use of readily available terminal alkynes and a catalytic amount of a silver salt with N-chlorosuccinimide as the chlorinating agent under mild conditions. Compared with the existing process, this method has a broad substrate scope: 19 examples were explored, and the products were obtained in excellent yields and were easily isolated by vacuum distillation. Moreover, recycling of the catalyst was achieved by simple filtration and desiccation, which made the method more economic and environmentally benign.
- Shi, Dunfa,Liu, Zhiwen,Zhang, Ziyu,Shi, Wei,Chen, Hao
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p. 1424 - 1426
(2015/06/10)
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- Highly enantioselective copper(i)-catalyzed conjugate addition of 1,3-diynes to α,β-unsaturated trifluoromethyl ketones
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The conjugate diynylation of α,β-unsaturated trifluoromethyl ketones is carried out in the presence of a low catalytic load (2.5 mol%) of a copper(i)-MeOBIPHEP complex, triethylamine and a terminal 1,3-diyne. Pre-metalation of the terminal 1,3-diyne with stoichiometric or higher amounts of dialkylzinc reagent is not required. The corresponding internal diynes bearing a propargylic stereogenic center are obtained with good yields and excellent enantioselectivities. This journal is
- Sanz-Marco, Amparo,Blay, Gonzalo,Mu?oz, M. Carmen,Pedro, José R.
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p. 8958 - 8961
(2015/05/27)
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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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- Electrophilic cyclization of aryldiacetylenes in the synthesis of functionalized enediynes fused to a heterocyclic core
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An efficient strategy for the synthesis of asymmetrically substituted enediynes fused to benzothiophene, benzofuran, and indole was developed. The proposed approach is based on the electrophilic cyclization of diacetylenes and Sonogashira coupling. Thus, iodocyclization of readily available ortho-functionalized (buta-1,3-diynyl)arenes was used as a direct way for the synthesis of 2-ethynyl-3-iodoheteroindenes. These substrates and their modified derivatives were easily converted by Sonogashira coupling with acetylenes to a variety of asymmetrically substituted acyclic enediynes fused to heterocycles. The tolerance of the developed methodology to a variety of functional groups is a great advantage in the synthesis of macrocyclic enediyne systems fused to a heterocyclic core. Synthesis of indole-fused 12-membered macrocyclic dienediyne was achieved using ring-closing metathesis as a key step.
- Danilkina,Kulyashova,Khlebnikov,Br?se,Balova
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p. 9018 - 9045
(2015/01/08)
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- Copper-catalyzed aerobic oxidative transformation of ketone- Derived N-tosyl hydrazones: An entry to alkynes
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A novel strategy involving Cu-catalyzed oxidative transformation of ketone-derived hydrazone moiety to various synthetic valuable internal alkynes and diynes has been developed. This method features inexpensive metal catalyst, green oxidant, good functional group tolerance, high regioselectivity and readily available starting materials. Oxidative deprotonation reactions were carried out to form internal alkynes and symmetrical diynes. Cross-coupling reactions of hydrazones with halides and terminal alkynes were performed to afford functionalized alkynes and unsymmetrical conjugated diynes. A mechanism proceeding through a Cu-carbene intermediate is proposed for the CC triple bond formation.
- Li, Xianwei,Liu, Xiaohang,Chen, Huoji,Wu, Wanqing,Qi, Chaorong,Jiang, Huanfeng
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supporting information
p. 14485 - 14489
(2015/02/05)
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- A mild CuI-catalyzed Glaser-type homo-coupling reaction using α,α-dibromo-β-dicarbonyl compounds as oxidants
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Exploration of α,α-dibromo-β-dicarbonyl compounds as novel organic oxidants for the mild Cu(I)-catalyzed Glaser-type homo-coupling reaction has been achieved, which provides an alternatively efficient pathway for the construction of 1,3-conjugated structures. In addition, the mechanism of this reaction was investigated.
- Fan, Xiaohui,Li, Na,Shen, Tong,Cui, Xiao-Meng,Lv, Hao,Zhu, Hong-Bo,Guan, Yong-Hong
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supporting information
p. 256 - 261
(2014/01/06)
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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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- 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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- Synthesis of fluoro- and perfluoroalkyl arenes via palladium-catalyzed [4 + 2] benzannulation reaction
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An efficient entry into densely substituted fluorinated and perfluoroalkylated benzene derivatives via chemo- and regioselective Pd-catalyzed [4 + 2] cross-benzannulation is presented. The synthetic utility of these products for the synthesis of various aromatic and heteroaromatic compounds is also demonstrated. This strategy offers a viable and quite general alternative to existing fluorination and perfluoroalkylation methods for securing these valuable molecules.
- Zatolochnaya, Olga V.,Gevorgyan, Vladimir
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supporting information
p. 2562 - 2565
(2013/06/26)
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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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- Palladium supported on amine-functionalized mesoporous silica: Highly efficient phosphine-free catalyst for alkyne-alkyne cross-coupling reaction
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An amine-functionalized mesoporous silica SBA-15 supported palladium catalyst was prepared and characterized. For the first time, this supported palladium has been used as an efficient phosphine-free and reusable catalyst for the cross-coupling of haloalkynes with terminal alkynes. A variety of haloalkynes and aromatic/aliphatic terminal alkynes were selectively coupled to afford unsymmetrical 1,4-disubstituted 1,3-diynes in good yields.
- Li, Hongling,Wang, Lailai,Yang, Min,Qi, Yanxing
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experimental part
p. 179 - 183
(2012/02/16)
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- Practical oxidative homo- and heterocoupling of terminal alkynes catalyzed by immobilized copper in MCM-41
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A practical oxidative homo- and heterocoupling of terminal alkynes was achieved in CH2Cl2 at 25 °C by using a 3-(2-aminoethylamino)propyl-functionalized MCM-41-immobilized copper(I) complex (MCM-41-2N-CuI, 1 mol-%) as the catalyst, piperidine (0.1 or 3 equiv.) as the base, and air as the environmentally friendly co-oxidant, yielding a variety of symmetrical and unsymmetrical 1,4-disubstituted 1,3-diynes in good to excellent yields. This heterogeneous copper catalyst showed a higher catalytic activity than CuI and can be recovered and recycled by a simple filtration of the reaction mixture and used for at least 10 consecutive runs without any decrease in activity. A practical oxidative homo- and heterocoupling of terminal alkynes was achieved in CH2Cl2 at 25 °C by using a 3-(2-aminoethylamino)propyl-functionalized MCM-41-immobilized copper(I) complex (MCM-41-2N-CuI, 1 mol-%) as the catalyst and air as the environmentally friendly oxidant, yielding a variety of symmetrical and unsymmetrical 1,4-disubstituted 1,3-diynes in good to excellent yields.
- Xiao, Ruian,Yao, Ruiya,Cai, Mingzhong
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experimental part
p. 4178 - 4184
(2012/09/22)
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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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- Carbon dioxide-mediated synthesis of 3(2H)-furanones from diyne alcohols
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A novel type of carbon dioxide-mediated reaction of diyne alcohols without any metal catalysts was reported. Carbon dioxide held the key to the success of this reaction, in which 3(2H)-furanones were selectively obtained in moderate to high yields.
- Yuan, Gaoqing,He, Zaijun,Zheng, Junhua,Chen, Zhengwang,Huang, Huawen,Shi, Dabin,Qi, Chaorong,Jiang, Huanfeng
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supporting information; experimental part
p. 5956 - 5959
(2011/11/28)
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- An efficient copper-catalyzed homocoupling of terminal alkynes to give symmetrical 1,4-disubstituted 1,3-diynes
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A facile and efficient pathway for the copper iodide and ligand N,N,N',N'-tetramethylethane-1,2-diamine promoted homocoupling reaction of terminal alkynes under ambient temperature and air as an oxidant was reported. The alkynes, including aromatic alkynes and aliphatic alkynes, could afford the symmetrical 1,4-disubstituted 1,3-diynes in good to excellent yields. Copyright
- Zhang, Songlin,Liu, Xiaoyan,Wang, Tongqiang
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supporting information; experimental part
p. 1463 - 1466
(2011/08/07)
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- Homo and heterocoupling of terminal alkynes using catalytic CuCl 2 and DBU
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Homocoupling of terminal alkynes has been efficiently achieved using catalytic amounts of CuCl2 and DBU. This methodology could be extended to couple two different terminal alkynes together by taking one of the alkyne partners, preferably the electron rich alkyne, in five fold excess than the other. CSIRO 2011.
- Balamurugan, Rengarajan,Naveen, Naganaboina,Manojveer, Seetharaman,Nama, Masthan Vali
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experimental part
p. 567 - 575
(2012/01/02)
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- From highly enantioselective catalytic reaction of 1,3-diynes with aldehydes to facile asymmetric synthesis of polycyclic compounds
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(S)-1,1′-Binaphth-2-ol (BINOL) in combination with ZnEt2, Ti(OiPr)4, and biscyclohexylamine was found to catalyze the highly enantioselective (83-95% ee) addition of various 1,3-diynes to aldehydes of diverse structures. This method provides a convenient pathway to generate a number of optically active dienediynes as the acyclic precursors to polycyclic compounds. The chiral dienediynes undergo highly chemoselective Pauson-Khand (PK) cycloaddition in benzaldehyde by using [Rh(cod)Cl]2 as the catalyst in the presence of rac-BINAP. High diastereoselectivity (up to >20:1) has also been achieved with the chiral dienediyne substrates containing a bulky substituent adjacent to the chiral center. In the presence of the Grubbs II catalyst, ring-closing enyne metathesis of the PK cycloaddition products led to the formation of the desired 5,5,7- and 5,5,8-fused tricyclic compounds. Further highly diastereoselective Diels-Alder reaction of a 5,5,7-tricyclic compound with maleic anhydride produced a 5,5,7,6-polycyclic product. The asymmetric synthesis of polycyclic compounds from optically active dienediynes has established a novel and efficient synthetic route to the structural framework of many biologically significant molecules.
- Turlington, Mark,Du, Yuhao,Ostrum, Samuel G.,Santosh, Vishaka,Wren, Kathryne,Lin, Tony,Sabat, Michal,Pu, Lin
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p. 11780 - 11794
(2011/09/16)
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- Iron/copper promoted oxidative homo-coupling reaction of terminal alkynes using air as the oxidant
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An inexpensive catalytic system, which used a readily available Fe(acac)3 and trace quantity of Cu(acac)2 as the co-catalyst and air as the oxidant for the homo-coupling of terminal alkynes, has been developed. The catalytic system could also apply to the cross-coupling reaction of two different terminal alkynes.
- Meng, Xu,Li, Chuanbin,Han, Baochun,Wang, Tiansheng,Chen, Baohua
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supporting information; scheme or table
p. 4029 - 4031
(2010/07/06)
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- Efficient copper(II) acetate catalyzed homo- and heterocoupling of terminal alkynes at ambient conditions
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Symmetrical 1,3-diynes were obtained in quantitative yields using the copper(II) acetate catalyzed homocoupling of terminal alkynes in the presence of a stoichiometric amount of piperidine at 25 °C under aerobic conditions. We also accomplished facile syntheses of unsymmetric 1,3-diynes by heterocoupling terminal alkynes in very good yields under the reported reaction conditions. Georg Thieme Verlag Stuttgart.
- Balaraman, Kaluvu,Kesavan, Venkitasamy
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experimental part
p. 3461 - 3466
(2010/11/21)
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- An efficient approach to homocoupling of terminal alkynes: Solvent-free synthesis of 1,3-diynes using catalytic Cu(II) and base
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We report an environmentally friendly, efficient method for transforming terminal acetylenes into 1,3-diynes based on catalytic amounts of a Cu(ii) salt and base under solvent-free conditions. The developed process conforms to the principles of 'green' chemistry and addresses the shortage of such methods for the synthesis of 1,3-diynes. The reaction is quite general and results in good yields. Interestingly, the system also allows the synthesis of unsymmetric 1,3-diynes by cross-coupling of two different terminal alkynes. Finally, the catalyst can also be recycled.
- Wang, Dong,Li, Jihui,Li, Na,Gao, Tingting,Hou, Sihua,Chen, Baohua
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supporting information; experimental part
p. 45 - 48
(2010/05/17)
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- Nickel-catalyzed oxidative coupling reactions of two different terminal alkynes using O2 as the oxidant at room temperature: Facile syntheses of unsymmetric 1,3-diynes
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(Formula Presented) Two different terminal alkynes now can be coupled together in the presence of NiCl2-6H2O/Cul by using an excess of one of the terminal alkyne substrates. The new method employed 20 mol % TMEDA as the ligand and environmentally benign O2 or air as the oxidant. It is the first example using Ni-salt as catalyst by employing air or O2 as oxidant, which led to efficient heterocoupling of two different alkynes.
- Yin, Weiyan,He, Chuan,Chen, Mao,Zhang, Heng,Lei, Aiwen
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scheme or table
p. 709 - 712
(2009/08/12)
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- Investigation of an efficient palladium-catalyzed C(sp)-C(sp) cross-coupling reaction using phosphine-olefin ligand: Application and mechanistic aspects
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A π-acceptor phosphine-electron-deficient olefin ligand was found effective in promoting Pd-catalyzed C(sp)-C(sp) cross-coupling reactions. The new protocol realized the cross-coupling of a broad scope of terminal alkynes and haloalkynes in good to excellent yields with high selectivities. Electron-rich alkynes, which are normally difficult substrates in Glaser couplings, could be employed as either nucleophiles or electrophiles. Alkynes bearing similar substituents, such as n-C5H11CCBr and n-C4H9CCH, which usually suffer from homocoupling side reactions under Cadiot-Chodkiewicz conditions, were successfully cross-coupled in the system. Preliminary kinetic studies revealed that the reaction rate was zero-order in the concentrations of both haloalkynes and terminal alkynes and first order in the loading of Pd(dba)2 and exhibited no obvious dependence on the loading of the copper salt. Control experiments with other phosphines such as PPh3 and DPPF as the ligand were carried out. All the kinetic evidence indicated that the phosphine-olefin ligand facilitated the reductive elimination in the catalytic cycle.
- Shi, Wei,Luo, Yingdong,Luo, Xiancai,Chao, Lei,Zhang, Heng,Wang, Jian,Lei, Aiwen
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supporting information; experimental part
p. 14713 - 14720
(2009/02/08)
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- Synthesis and solid-state polymerization of triyne and enediyne derivatives with similar π-conjugated structures
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Three diacetylene monomer model compounds with similar π-conjugation systems, 10-phenyl-5,7,9-decatriynyl W-phenylcarbamate (1), (E)-10-phenyldec-9- en-5,7-diynyl /V-phenylcarbamate (2), and (E)-10-phenyldec-5-en-7,9-diynyl N-phenylcarbamate (3), were synthesized and their properties and solid-state polymerization were investigated. Based on the absorption spectra of the monomers, it was found that the conjugation effect of a double bond was different from that of a triple bond in solution. Monomers 1,2, and 3 gave one, two, and five crystal forms, respectively, of which 1 and one of the crystal forms of 2 (2a) could be polymerized in the solid state. The conversions after y-ray irradiation (1 MGy dose) were 53% and 20%, respectively. The longest-wavelength absorption maxima of the polymers prepared from 1 and 2a were 645 and 655 nm, respectively. The polymerizable crystals 1 and 2a were found to have layered monomer structures with spacing of 3.1-3.6 nm. Based on solid-state 13CNMR spectra, the polymerization sites of 1 were determined to be the 1,4- and 3,6-positions with respect to the phenyl ring, and that of 2a was determined to be the 3,6-position with respect to the phenyl ring.
- Mizukoshi, Kana,Okada, Shuji,Kimura, Tatsumi,Shimada, Satoru,Matsuda, Hiro
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body text
p. 1028 - 1037
(2009/04/13)
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- Copper-catalyzed cross-coupling reactions of bromoalkynols with terminal alkynes in supercritical carbon dioxide
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Copper-catalyzed cross-coupling reactions of bromoalkynols and terminal alkynes were carried out in supercritical carbon dioxide (scCO2) to afford the corresponding unsymmetrical diynes with good yields. The reaction is sensitive to temperature and the pressure of CO2. Methanol, as a cosolvent of scCO2, could promote dissolution of the inorganic salt and thus facilitated the reaction. This new heterocoupling reaction system is more environmentally friendly than more traditional methods, since it uses scCO2 as solvent and sodium acetate as base instead of amines. Georg Thieme Verlag Stuttgart.
- Jiang, Huan-Feng,Wang, A.-Zhong
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p. 1649 - 1654
(2008/02/05)
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- Are terminal aryl butadiynes stable? Synthesis and X-ray crystal structures of a series of aryl- and heteroaryl-butadiynes (Ar-C≡C-C≡C-H)
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The synthesis and isolation are reported of a range of terminal aryl- and heteroaryl-butadiynes (ArC≡C-C≡CH) 4a-h from 2-methyl-6-(aryl/ heteroaryl)hexa-3,5-diyn-2-ol precursors. The stability of 4a-h in solution is concentration dependent: many of the de
- West, Kara,Wang, Changsheng,Batsanov, Andrei S.,Bryce, Martin R.
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p. 8541 - 8544
(2007/10/03)
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- Contingency and Serendipity in the Reactions of Fischer Carbene Complexes with Conjugated Triynes
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The first examples of reactions of Fischer carbene complexes with triynes are reported. The regioselectivity of the reaction of the two different alkyne functions in the symmetrical triyne depends on the nature of the substituent of the triyne. Bis-silyl-substituted triynes react at the central alkyne unit, whereas bis-aryl- and bis-alkyl-substituted triynes react at the end alkyne unit. The reaction of a Fischer carbene complex with a phenyl substituent also reacts with a bis-silyl-substituted triyne at the central alkyne unit but gives a furan product rather than the normal phenol product. It was also demonstrated that all three of the alkyne units in conjugated triynes could react in turn with a Fischer carbene complex to give access to trisquinones. Copyright
- Jiang, May Xiao-Wu,Rawat, Manish,Wulff, William D.
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p. 5970 - 5971
(2007/10/03)
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- Novel Synyhesis of Unsymmetrical Diarylbutadiynes
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Terminal arylbutadiynes, derived from 6-aryl-3,5-hexadin-2-ols, undergo a ready palladium-catalyzed coupling with activated aryl halides in the presence of a phase transfer catalyst to unsymmetrical diarylbutadiynes, not easily available by other coupling
- Nye, Susan Adams,Potts, Kevin T.
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p. 375 - 377
(2007/10/02)
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