- Hydrazone–Cu-Catalyzed Suzuki–Miyaura-Type Reactions of Dibromoalkenes with Arylboronic Acids
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We have found that Suzuki–Miyaura-type reactions of dibromoalkenes with arylboronic acids using a hydrazone–Cu catalyst system proceeded smoothly under mild conditions to afford the corresponding internal alkyne derivatives in good yields. Furthermore, we also succeeded in the synthesis of o-allyloxy(ethynyl)benzene derivatives, which are known to be effective precursors of various heterocyclic compounds, through this reaction.
- Watanabe, Kohei,Mino, Takashi,Hatta, Chikako,Ishikawa, Eri,Yoshida, Yasushi,Sakamoto, Masami
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- Gold-Catalyzed Cyclization of 2-Alkynylaldehyde Cyclic Acetals via Hydride Shift for the Synthesis of Indenone Derivatives
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An efficient gold-catalyzed cyclization of 2-alkynylaldehyde cyclic acetals has been developed for the synthesis of indenone derivatives. A wide variety of functionalized indenone derivatives can be obtained in good-to-excellent yields. HMBC and NOESY NMR analyses and mechanistic elucidation experiments revealed that the cyclization occurs via a 1,5-H shift. The cyclic acetal group promoted the 1,5-H shift by activating the benzylic C-H bond and preventing the migration of the alkoxy group by tethering both alkoxy groups.
- Yamada, Tsuyoshi,Park, Kwihwan,Tachikawa, Takumu,Fujii, Akiko,Rudolph, Matthias,Hashmi, A. Stephen K.,Sajiki, Hironao
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supporting information
p. 1883 - 1888
(2020/03/03)
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- A carrier-free and recyclable protocol for the cross-coupling of terminal alkynes with arylboronic acids in H2O/TBAB
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A new and recyclable protocol was developed for Pd(OAc)2-catalyzed the cross-coupling reaction of terminal alkynes with arylboronic acids using environmentally friendly H2O/TBAB as reaction medium. A series of cross-coupling products containing internal acetylenic bond can be obtained with good selectivity and yield. The Pd(OAc)2/H2O/TBAB system was stable in the Sonogashira-type cross-coupling reaction and could be used at least three cycles without considerable decrease in catalytic performance. The results suggest that the unsupported and recyclable systems can be extended to the other realm of C&C bond formation in synthetic organic chemistry.
- Tang, Bo-Xiao,Kuang, Ren-Yun,Wen, Ji-Wu,Huang,Zhang, Zhen-Xing,Shen, Yu-Jun,Chen, Jia-Ping,Wu, Wen-Ying
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p. 1975 - 1977
(2019/07/03)
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- Preparation and catalytic properties of the triphenylarsine and triphenylstibine-stabilized tri-heteroleptic NHC–Pd?allyl complexes
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A series of triphenylarsine and triphenylstibine-stabilized tri-heteroleptic NHC–Pd?allyl complexes were synthesized and characterized. The solid-state structures of the complexes shown mononuclear carbene palladium complexes, in which, each palladium cen
- Yang, Jin
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- Gold-Catalyzed Dimerization of Diarylalkynes: Direct Access to Azulenes
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We have developed a simple gold-catalyzed procedure for the synthesis of substituted and modifiable azulenes. The azulenes are formed either by the dimerization of push–pull diarylalkynes bearing a fluorine atom in ortho or para position or by the dimeriz
- Claus, Vanessa,Schukin, Michael,Harrer, Siegfried,Rudolph, Matthias,Rominger, Frank,Asiri, Abdullah M.,Xie, Jin,Hashmi, A. Stephen K.
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supporting information
p. 12966 - 12970
(2018/09/25)
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- Synthesis of o-Allyloxy(ethynyl)benzene Derivatives by Cu-Catalyzed Suzuki–Miyaura-Type Reaction and Their Transformations into Heterocyclic Compounds
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We have found that Suzuki–Miyaura-type reactions of o-allyloxy(bromoethynyl)benzenes with arylboronic acids using a hydrazone/Cu catalyst system proceeded smoothly in iPrOH under mild conditions to afford the corresponding o-allyloxy(arylethynyl)benzene derivatives in good yields without decomposition of the allyloxy group. We have further demonstrated that annulation and enyne metathesis of the o-allyloxy(arylethynyl)benzene derivatives using transition-metal catalysts led to various heterocyclic compounds.
- Watanabe, Kohei,Mino, Takashi,Ishikawa, Eri,Okano, Miyu,Ikematsu, Tatsuya,Yoshida, Yasushi,Sakamoto, Masami,Sato, Kazuki,Yoshida, Kazuhiro
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p. 2359 - 2368
(2017/05/01)
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- Three-Component One-Pot Synthesis of Unsymmetrical Diarylalkynes by Thermocontrolled Sequential Sonogashira Reactions Using Potassium Ethynyltrifluoroborate
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Unsymmetrical diarylalkynes were synthesized in moderate to good yields through a three-component one-pot procedure involving thermocontrolled sequential Sonogashira reactions with potassium ethynyltrifluoroborate and two different reactive aryl halides. The one-pot procedure was initiated by the palladium/copper-catalyzed Sonogashira coupling of potassium ethynyltrifluoroborate to an aryl iodide or electron-deficient aryl bromide at 40 °C. Following a subsequent deboronative Sonogashira reaction of the in situ generated potassium (arylethynyl)trifluoroborate, a second coupling to a less-active electron-rich aryl bromide at 80 °C, without any additional palladium/copper catalyst or base, gave rise to unsymmetrical diarylalkynes.
- Kim, Taejung,Jeong, Kyu Hyuk,Kim, Youngseok,Noh, Taesub,Choi, Jaeyoung,Ham, Jungyeob
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p. 2425 - 2431
(2017/05/12)
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- Palladium-catalyzed deacetonative coupling of aryl propargylic alcohols with aryl chlorides in water
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A highly efficient and green process for palladium-catalyzed deacetonative coupling of aryl propargylic alcohols with aryl chlorides has been developed. The reaction occurs smoothly in neat water with 2 mol% PdCl2 as catalyst, and various synthetically useful functional groups, including ether, aldehyde, ketone, and heterocyclics, are well tolerated. Moreover, the reaction could proceed through a consecutive Sonogashira/deacetonative process using 2-methyl-3-butyn-2-ol and aryl chlorides as coupling partners, affording the symmetric alkynes in good yields.
- Chang, Feng,Liu, Yanping
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supporting information
p. 961 - 967
(2017/05/04)
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- An N-heterocyclic carbene based MOF catalyst for Sonogashira cross-coupling reaction
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The post-synthetic modification of azolium containing MOFs generated a new heterogeneous N-heterocyclic carbene catalyst (1-Pd), which is very active for Sonogashira cross coupling reaction.
- Ezugwu, Chizoba I.,Mousavi, Bibimaryam,Asrafa, Md. Ali,Mehta, Akshay,Vardhan, Harsh,Verpoort, Francis
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p. 2050 - 2054
(2016/04/26)
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- Green synthesis of Pd/Fe3O4 nanoparticles using Euphorbia condylocarpa M. bieb root extract and their catalytic applications as magnetically recoverable and stable recyclable catalysts for the phosphine-free Sonogashira and Suzuki co
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This work reports on the green synthesis of Pd/Fe3O4 nanoparticles using Euphorbia condylocarpa M. biebroot extract as reducing agents and stabilizers and their catalytic applications in ligand- and copper-free Sonogashira and Suzuki
- Nasrollahzadeh, Mahmoud,Mohammad Sajadi,Rostami-Vartooni, Akbar,Khalaj, Mehdi
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- Green synthesis of Pd/Fe3O4 nanoparticles using Euphorbia condylocarpa M. bieb root extract and their catalytic applications as magnetically recoverable and stable recyclable catalysts for the phosphine-free Sonogashira and Suzuki co
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This work reports on the green synthesis of Pd/Fe3O4 nanoparticles using Euphorbia condylocarpa M. bieb root extract as reducing agents and stabilizers and their catalytic applications in ligand- and copper-free Sonogashira and Suzuk
- Nasrollahzadeh, Mahmoud,Mohammad Sajadi,Rostami-Vartooni, Akbar,Khalaj, Mehdi
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- Palladium nanoparticles catalyzed Sonogashira reactions for the one-pot synthesis of symmetrical and unsymmetrical diarylacetylenes
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A variety of symmetrical and unsymmetrical diarylacetylenes are synthesized by ligand-free palladium nanoparticles catalyzed copper-free and amine-free Sonogashira cross-coupling reactions between aryl iodides and trimethylsilylacetylene (TMSA) under mild reaction conditions.
- Mandali, Pavan Kumar,Chand, Dillip Kumar
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- Palladium on nano-magnetite: A magnetically reusable catalyst in the ligand- and copper-free Sonogashira and Stille cross-coupling reactions
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This paper reports on the synthesis and use of palladium on nano-magnetite as a magnetically separable catalyst for copper- and ligand-free Songashira and Stille coupling reactions. The catalyst was characterized using powder XRD, SEM, EDS and VSM techniques. This method has the advantages of high yields, simple methodology and easy work-up. Catalytic efficiency remains unaltered even after several repeated cycles.
- Nasrollahzadeh, Mahmoud,Maham, Mehdi,Ehsani, Ali,Khalaj, Mehdi
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p. 19731 - 19736
(2014/05/20)
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- The copper-free Sonogashira cross-coupling reaction promoted by palladium complexes of nitrogen-containing chelating ligands in neat water at room temperature
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The commercially available 2,2′-dipyridylamine was used as a supporting ligand in the palladium-catalyzed Sonogashira cross-coupling reaction. The reactions between aryl iodides and terminal alkynes with different steric hindrance can be efficiently performed in the absence of copper in neat water at room temperature. The superior catalytic performance of the catalytic system was attributed to water solubility of the palladium 2,2′- dipyridylamine complex. Palladium nanoparticles with small size and narrow size distribution were formed after the cross-coupling reaction.
- Zhong, Hong,Wang, Jinyun,Li, Liuyi,Wang, Ruihu
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p. 2098 - 2103
(2014/01/17)
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- Palladacycle-catalyzed deacetonative sonogashira coupling of aryl propargyl alcohols with aryl chlorides
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An efficient and general protocol for the deacetonative Sonogashira coupling of aryl propargyl alcohols with aryl chlorides is described. The reaction proceeded smoothly with the catalyst system of palladacycle/Xphos. This result represents the first succ
- Hu, Hao,Yang, Fan,Wu, Yangjie
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p. 10506 - 10511
(2013/11/06)
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- Palladacycle-catalyzed decarboxylative coupling of alkynyl carboxylic acids with aryl chlorides under air
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A highly efficient and practical protocol for palladacycle-catalyzed decarboxylative coupling of alkynyl carboxylic acids with aryl chlorides was developed. The reaction could proceed smoothly in air within 3 h under optimized reaction conditions (1 mol % of palladacycle, 4 mol % of Xphos, 2.0 equiv of K2CO3 in xylene/H2O), affording the corresponding internal alkynes in mostly good to excellent yields. Remarkably, this result represents the first successful examples of this type of decarboxylative cross-coupling using electron-poor, electron-neutral and even inactive sterically hindered electron-rich aryl chlorides as the starting materials.
- Li, Xi'Ang,Yang, Fan,Wu, Yangjie
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p. 4543 - 4550
(2013/06/05)
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- Microwave-promoted copper-free Sonogashira-Hagihara couplings of aryl imidazolylsulfonates in water
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Aryl imidazol-1-ylsulfonates have been efficiently cross-coupled with aryl-, alkyl-, and silylacetylenes in neat water under copper-free conditions at 110 °C assisted by microwave irradiation. Using 0.5mol% of an oxime palladacycle as precatalyst, 2-dicyclohexylphosphino-2′,6′- dimethoxybiphenyl (SPhos, 2mol%) as ligand, hexadecyltrimethylammonium bromide (CTAB) as additive, and triethylamine (TEA) as base, a wide array of disubstituted alkynes has been prepared in good to high yields in only 30min. Copyright
- Civicos, Jose F.,Alonso, Diego A.,Najera, Carmen
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supporting information
p. 203 - 208
(2013/03/14)
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- Heck and Sonogashira cross-coupling reactions using recyclable Pd-Fe 3O4 heterodimeric nanocrystal catalysts
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We have developed a convenient Pd-Fe3O4 heterodimeric nanocrystal catalyst system for Heck and Sonogashira reactions. This catalyst offers an environment-friendly, atom-efficient, and robust catalytic system for both reactions. Furthermore the nanocrystal catalyst could be easily separated by an external magnet and recycled six times without losing its catalytic activity.
- Chung, Jooyoung,Kim, Jinju,Jang, Youngjin,Byun, Sangmoon,Hyeon, Taeghwan,Kim, B. Moon
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p. 5192 - 5196
(2013/09/02)
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- Synthesis of 1,2-disubstituted acetylenes via copper-catalyzed Suzuki coupling of organoboronic acids with 1,1-dibromo-1-alkenes
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An efficient synthesis of 1,2-disubstituted acetylenes has been described. Reactions of organoboronic acids with 1,1-dibromo-1-alkenes in the presence of a catalytic amount of CuI (10 mol %), 8-hydroxyquinoline (10 mol %), and using potassium phosphate as base in C2H5OH afforded the desired 1,2-disubstituted acetylenes in good to excellent yields. It is important to note that the formation of 1,3-diynes, which are derived from the homocoupling of 1,1-dibromo-1-alkenes, can be almost completely suppressed under these optimized conditions.
- Liu, Jidan,Dai, Fenglin,Yang, Zhiyong,Wang, Sizhuo,Xie, Kai,Wang, Anwei,Chen, Xiang,Tan, Ze
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p. 5678 - 5683
(2015/04/15)
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- Highly active palladium catalyst for the sonogashira coupling reaction of unreactive aryl chlorides
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This communication reports on the β-diketiminatophosphane palladium-catalyzed copper-free Sonogashira coupling of aryl chlorides with alkynes. A catalyst loading of 0.5 mol% is sufficient to achieve high performance under relatively mild reaction conditio
- Lee, Dong-Hwan,Kwon, Young-Jun,Jin, Myung-Jong
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supporting information; experimental part
p. 3090 - 3094
(2012/01/03)
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- Phosphane-free copper-catalyzed decarboxylative coupling of alkynyl carboxylic acids with aryl halides under aerobic conditions
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A phosphane-free copper-catalyzed decarboxylative cross-coupling reaction of alkynyl carboxylic acids with aryl halides was developed. CuBr (1-5 mol-%) was used as a catalyst in the presence of a β-diketone ligand in air. The reactions of aryl iodides wer
- Pan, Delin,Zhang, Chun,Ding, Shengtao,Jiao, Ning
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supporting information; experimental part
p. 4751 - 4755
(2011/10/08)
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- Direct synthesis of alkynylstannanes: ZnBr2 catalyst for the reaction of tributyltin methoxide and terminal alkynes
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Metal hopping: Various alkynylstannanes were synthesized by the direct reaction of Bu3SnOMe with terminal alkynes at room temperature in the presence of a ZnBr2 catalyst. Rather than acting as a Lewis acid, ZnBr2 was transmetalated with Bu3SnOMe to give Zn(OMe)2, which is key to the catalytic reaction. Copyright
- Kiyokawa, Kensuke,Tachikake, Nodoka,Yasuda, Makoto,Baba, Akio
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experimental part
p. 10393 - 10396
(2011/12/04)
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- 2,2'-diamino-6,6'-dimethylbiphenyl as an efficient ligand in the CuI-catalyzed sonogashira reaction of aryl iodides and bromides with terminal alkynes
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2,2'-Diamino-6,6'-dimethylbiphenyl (L1) was found to be a good ligand in the CuI-catalyzed Sonogashira coupling reaction of various aryl iodides and bromides with terminal alkynes. Under suitable conditions, all reactions gave the desired coupling product
- Wang, Bin-Bin,Ye, Yue-Mei,Chen, Jun-Jun,Zhou, Xia-Xia,Lu, Jian-Mei,Shao, Li-Xiong
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experimental part
p. 526 - 530
(2011/06/25)
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- One-pot procedure for the synthesis of unsymmetrical diarylalkynes
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Unsymmetrical diarylalkynes are accessible by a one-pot procedure from two different aryl halides and (trimethylsilyl)acetylene. The three-component coupling is initialized by a Pd/Cu-catalyzed Sonogashira coupling of an aryl halide with (trimethylsilyl)a
- Severin, Rene,Reimer, Jessica,Doye, Sven
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supporting information; experimental part
p. 3518 - 3521
(2010/07/17)
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- Perfluoro-tagged, phosphine-free palladium nanoparticles supported on silica gel: Application to alkynylation of aryl halides, Suzuki-Miyaura cross-coupling, and Heck reactions under aerobic conditions
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The utilization of perfluoro-tagged palladium nanoparticles immobilized on fluorous silica gel through fluorous-fluorous interactions (Pd np-A/FSG) or through covalent bonding to silica gel (Pd np-B) in the alkynylation of aryl halides, in the Suzuki-Miyaura cross-coupling, as well as in the Heck reaction between methyl acrylate and aryl iodides is described. The reactions are carried out under aerobic and phosphine-free conditions with excellent to quantitative product yields in each case. The catalysts are easily recovered and reused several times without significant loss of activity. The alkynylation of aryl halides (under copper-free conditions) and the Suzuki-Miyaura cross-coupling are carried out in water. The Heck reaction of methyl acrylate with aryl iodides is best performed in MeCN. The utilization of Pdnp-B in the synthesis of 2,3-disubstituted indoles from 2-(alkynyl)trifluoroacetanilides and aryl halides is also reported.
- Bernini, Roberta,Cacchi, Sandro,Fabrizi, Giancarlo,Forte, Giovanni,Petrucci, Francesco,Prastaro, Alessandro,Niembro, Sandra,Shafir, Alexandr,Vallribera, Adelina
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supporting information; experimental part
p. 150 - 158
(2010/05/18)
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- Alkynylation of aryl halides with perfluoro-tagged palladium nanoparticles immobilized on silica gel under aerobic, copper- and phosphine-free conditions in water
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The utilization of perfluoro-tagged palladium nanoparticles immobilized on fluorous silica gel through fluorous-fluorous interactions (Pd np-A/FSG) or linked to silica gel by covalent bonds (Pd np-B) in the alkynylation of terminal a
- Bernini, Roberta,Cacchi, Sandro,Fabrizi, Giancarlo,Forte, Giovanni,Petrucci, Francesco,Prastaro, Alessandro,Niembro, Sandra,Shafir, Alexandr,Vallribera, Adelina
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supporting information; scheme or table
p. 2270 - 2273
(2009/09/26)
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- A general and simple synthesis of phosphindoles
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A first simple and general synthesis of phosphindoles by intramolecular cyclisation of secondary o-phosphinotolanes is described.
- Markl,Jin,Berr
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p. 3103 - 3106
(2007/10/02)
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