- Ynonylation of Acyl Radicals by Electroinduced Homolysis of 4-Acyl-1,4-dihydropyridines
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Herein we report the conversion of 4-Acyl-1,4-dihydropyridines (DHPs) into ynones under electrochemical conditions. The reaction proceeds via the homolysis of acyl-DHP under electron activation. The resulting acyl radicals react with hypervalent iodine(III) reagents to form the target ynones or ynamides in acceptable yields. This mild reaction condition allows wider functionality tolerance that includes halides, carboxylates, or alkenes. The synthetic utility of this methodology is further demonstrated by the late-stage modification of complex molecules.
- Luo, Xiaosheng,Wang, Ping
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p. 4960 - 4965
(2021/07/20)
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- Synthesis of Isoselenazoles and Isothiazoles from Demethoxylative Cycloaddition of Alkynyl Oxime Ethers
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A general method for the synthesis of isoselenazoles and isothiazoles has been developed by the base-promoted demethoxylative cycloaddition of alkynyl oxime ethers using the cheap and inactive Se powder and Na2S as selenium and sulfur sources. This transformation features the direct construction of N-, Se-, and S-containing heterocycles through the formation of N-Se/S and C-Se/S bonds in one-pot reactions with excellent functional group tolerance.
- Zhang, Zhu-Zhu,Chen, Rong,Zhang, Xiao-Hong,Zhang, Xing-Guo
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p. 632 - 642
(2020/12/22)
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- Base-Promoted Synthesis of Polysubstituted 4-Aminoquinolines from Ynones and 2-Aminobenzonitriles under Transition-Metal-Free Conditions
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A transition-metal-free and base-promoted one-pot reaction of ynones with 2-aminobenzonitriles is described. The reaction was initiated through sequential aza-Michael addition/intramolecular annulation to afford various multisubstituted 4-aminoquinolines
- Kumar, Ankit,Mishra, Pawan K.,Saini, Kapil Mohan,Verma, Akhilesh K.
-
supporting information
p. 2546 - 2551
(2021/03/16)
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- Bifunctional Borane Catalysis of a Hydride Transfer/Enantioselective [2+2] Cycloaddition Cascade
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Herein, we present a mild and efficient method for synthesizing enantioenriched tetrahydroquinoline-fused cyclobutenes through a cascade reaction between 1,2-dihydroquinolines and alkynones with catalysis by chiral spiro-bicyclic bisboranes. The bisborane
- Zhang, Ming,Wang, Xiao-Chen
-
supporting information
p. 17185 - 17190
(2021/07/06)
-
- Selective Thiocyanation and Aromatic Amination to Achieve Organized Annulation of Enaminone with Thiocyanate
-
A tandem insertion of thiocyanate to enamine was performed for the regioselective synthesis of multisubstituted benzoimidazo[2,1-b]thiazoles. This method was shown to be effective in addressing the issue of isomerization encountered in common strategies. With a change made to the leading group on the aniline fragment of enamine, the reaction achieved different transformations, thus enabling multisubstituted benzo[4,5]imidazo[2,1-b]thiazoles and thiazoles in satisfactory yields.
- Feng, Xukai,Leng, Xin,Li, Jianli,Li, Yao,Liu, Hua,Liu, Lang,Liu, Ping,She, Mengyao,Zhang, Jun,Zhang, Shengyong,Zheng, Tingting
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supporting information
p. 8396 - 8401
(2021/11/17)
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- Feeding Carbonylation with CO2via the Synergy of Single-Site/Nanocluster Catalysts in a Photosensitizing MOF
-
Solar-driven carbonylation with CO2 replacing toxic CO as a C1 source is of considerable interest; however it remains a great challenge due to the inert CO2 molecule. Herein, we integrate cobalt single-site and ultrafine CuPd nanocluster catalysts into a
- Fu, Shanshan,Guo, Guang-Chen,Guo, Song,Lu, Tong-Bu,Yao, Shuang,Yuan, Wenjuan,Zhang, Zhi-Ming
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p. 20792 - 20801
(2021/12/14)
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- Carboxyboronate as a Versatile In Situ CO Surrogate in Palladium-Catalyzed Carbonylative Transformations
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The application of carboxy-MIDA-boronate (MIDA=N-methyliminodiacetic acid) as an in situ CO surrogate for various palladium-catalyzed transformations is described. Carboxy-MIDA-boronate was previously shown to be a bench-stable boron-containing building block for the synthesis of borylated heterocycles. The present study demonstrates that, in addition to its utility as a precursor to heterocycle synthesis, carboxy-MIDA-boronate is an excellent in situ CO surrogate that is tolerant of reactive functionalities such as amines, alcohols, and carbon-based nucleophiles. Its wide functional-group compatibility is highlighted in the palladium-catalyzed aminocarbonylation, alkoxycarbonylation, carbonylative Sonogashira coupling, and carbonylative Suzuki–Miyaura coupling of aryl halides. A variety of amides, esters, (hetero)aromatic ynones, and bis(hetero)aryl ketones were synthesized in good-to-excellent yields in a one-pot fashion.
- Tien, Chieh-Hung,Trofimova, Alina,Holownia, Aleksandra,Kwak, Branden S.,Larson, Reed T.,Yudin, Andrei K.
-
supporting information
p. 4342 - 4349
(2020/12/25)
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- Visible-light-mediated photocatalytic cross-coupling of acetenyl ketones with benzyl trifluoroborate
-
In this report, we describe a simple visible light-triggered Barbier-type reaction by employing acetenyl ketones with benzyl trifluoroborates. Through a radical-radical cross-coupling process, this photocatalytic protocol furnished a wide range of tertiary propargyl alcohols. Mechanistic investigation indicated that proton-coupled electron transfer (PCET) might be involved in the photochemical transformations.
- Zhang, Lingchun,Chu, Yanle,Ma, Peizhi,Zhao, Shujuan,Li, Qiaoyan,Chen, Boya,Hong, Xuejiao,Sun, Jun
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supporting information
p. 1073 - 1077
(2020/02/22)
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- Alkyne derivative as well as preparation method and application thereof (by machine translation)
-
The invention belongs to the technical field of organic synthesis, and discloses an acetylenic ketone derivative and a preparation method and application thereof. The formula (I) is shown in the structural formula of the alkyne derivative. R1 And R2 Heterocyclyl groups of C1 - C20, halogen, ester, carbonyl, nitro, substituted amino, C5 - C30, or C5 - C30, respectively. To the strategy of nickel catalytic reduction coupling, a carboxylic acid derivative which is widely used in nature is used as a substrate, an alkyne halide is combined as an active alkynylation reagent, and under the condition of room temperature, the universality and the high efficiency method for rapidly constructing various substituted alkynes are obtained. The alkyne compound disclosed by the invention not only can be used as a practical synthesis, but also can be used as a precursor of heterocyclic compounds such as furan, pyrazole, quinoline, pyrimidine and the like. (by machine translation)
- -
-
Paragraph 0079-0084
(2020/06/05)
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- Recyclable heterogeneous palladium-catalyzed carbonylative Sonogashira coupling under CO gas-free conditions
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A convenient, efficient and practical heterogeneous palladium-catalyzed carbonylative Sonogashira coupling of aryl iodides with terminal alkynes under CO gas-free conditions has been developed by using an MCM-41-supported bidentate phosphine palladium ace
- Zhou, Zebiao,Li, Jianying,Xu, Zhaotao,Cai, Mingzhong
-
supporting information
p. 2015 - 2025
(2020/05/13)
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- Emission solvatochromic, solid-state and aggregation-induced emissive α-pyrones and emission-tuneable 1H-pyridines by Michael addition–cyclocondensation sequences
-
Starting from substituted alkynones, α-pyrones and/or 1H-pyridines were generated in a Michael addition–cyclocondensation with ethyl cyanoacetate. The peculiar product formation depends on the reaction conditions as well as on the electronic substitution
- Breuer, Natascha,Gruber, Irina,Janiak, Christoph,Müller, Thomas J.J.
-
supporting information
p. 2684 - 2703
(2019/12/11)
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- Synthesis of 1-Cyano-3-acylnaphthalenes via Formal [4+2] Benzannulation of 2-(2-Alkynylphenyl)acetonitriles and Alkynones
-
Effective transition-metal-free formal [4+2] benzannulation for the preparation of 1-cyano-3-acylnaphthalenes from 2-(2-alkynylphenyl)acetonitriles and alkynones through sequential C-C bond coupling has been developed. This protocol is characterized by mi
- Chen, Lu-Lu,Zhang, Jing-Wen,Yang, Wan-Wan,Fu, Ji-Ya,Zhu, Jun-Yan,Wang, Yan-Bo
-
p. 8090 - 8099
(2019/06/27)
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- Base-Controlled Divergent Synthesis of 5-Cyanobenzoxepines and Benzofuro[2,3- b]pyridines from 2-Bromophenylacetonitriles and Ynones
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An effective base-controlled divergent annulation reaction of 2-bromophenylacetonitriles and ynones has been developed. Various functionalized 5-cyanobenzoxepines and benzofuro[2,3-b]pyridines were obtained with a broad substrate scope and high regioselec
- Chen, Lu-Lu,Zhang, Jing-Wen,Chen, Pei,Zhang, Shuai,Yang, Wan-Wan,Fu, Ji-Ya,Zhu, Jun-Yan,Wang, Yan-Bo
-
supporting information
p. 5457 - 5461
(2019/08/01)
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- Palladium-Catalyzed Cascade Annulation/Allylation of Alkynyl Oxime Ethers with Allyl Halides: Rapid Access to Fully Substituted Isoxazoles
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A novel and efficient approach for the synthesis of functionalized isoxazoles via palladium-catalyzed cascade annulation/allylation of alkynyl oxime ethers with allyl halides has been established. The present protocol exhibits mild reaction conditions, good functional group compatibility, and convenient operation. Moreover, scalability was performed and further decoration of the isoxazole product was achieved.
- Li, Can,Li, Jianxiao,Zhou, Fei,Li, Chaosheng,Wu, Wanqing
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p. 11958 - 11970
(2019/10/11)
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- Synthesis of α,β-alkynyl ketones via the nickel catalysed carbonylative Sonogashira reaction using oxalic acid as a sustainable C1 source
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An efficient and economic nickel-dppb catalyzed, carbonylative Sonogashira cross-coupling reaction was demonstrated to provide rapid access to various α,β-alkynyl ketones from aryl iodides and terminal alkynes using oxalic acid as the ex situ C1 source in a double vial (DV) system. Notably, the role of the ligand in combination with the Ni catalyst for the selective formation of carbonylative Sonogashira products was investigated and supported with control experiments. Yet, no reports are available for carbonylative Sonogashira coupling by using a CO-surrogate under Ni-catalyzed conditions. In this process, for the first time, oxalic acid is used as an ex situ solid, bench stable, easy to handle and efficient CO surrogate in a DV-system for the carbonylative Sonogashira coupling reaction with vast substrate scope.
- Shaifali,Ram, Shankar,Thakur, Vandna,Das, Pralay
-
supporting information
p. 7036 - 7041
(2019/08/01)
-
- Visible-light-mediated dehydrogenative cross-coupling between terminal alkynes and aldehydes by employing a supramolecular polymeric ensemble of PBI derivative
-
A supramolecular polymer of PBI derivative and ZnO NPs has been developed which exhibits remarkable efficiency in direct dehydrogenative cross-coupling between terminal alkynes and aldehydes for the synthesis of ynones under photocatalytic conditions.
- Kataria, Meenal,Deol, Harnimarta,Singh, Gurpreet,Kumar, Manoj,Bhalla, Vandana
-
supporting information
p. 822 - 826
(2018/02/06)
-
- Diversity-oriented four-component synthesis of solid state luminescent difluoro oxazaborinines
-
(Hetero)aroyl chlorides, alkynes, anilines, and BF3 diethyl etherate are reacted in an alkynylation-amination-cyclization one-pot process to give trisubstituted difluoro oxazaborinines in moderate to very good yield in the sense of a consecutiv
- Dohe, Janis,Ko?mann, Janina,Müller, Thomas J.J.
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p. 198 - 217
(2018/05/22)
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- Merging " Anti-Baldwin" 3- Exo-Dig Cyclization with 1,2-Alkynyl Migration for Radical Alkylalkynylation of Unactivated Olefins
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A new combination of "anti-Baldwin" 3-exo-dig cyclization with 1,2-alkynyl migration of 1,4-enynes with simple cycloalkanes was established, enabling C-C breaking and reconstruction to access a wide range of α-alkynyl ketones with generally good yields by
- Zhao, Qi,Ji, Xiao-Shuang,Gao, Yi-Yun,Hao, Wen-Juan,Zhang, Ke-Ying,Tu, Shu-Jiang,Jiang, Bo
-
supporting information
p. 3596 - 3600
(2018/06/26)
-
- Consecutive Alkynylation-Michael Addition-Cyclocondensation (AMAC) Multicomponent Syntheses of α-Pyrones and α-Pyridones
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A novel consecutive three-component synthesis of α-pyrones is based upon an alkynylation-Michael addition-cyclocondensation (AMAC) sequence, starting from (hetero)aroyl chloride and terminal alkyne to furnish the alkynone which reacts with malonates to gi
- Breuer, Natascha,Müller, Thomas J. J.
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p. 2741 - 2752
(2018/06/08)
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- An effective preparation of both 1,3-diketones and nitriles from alkynones with oximes as hydroxide sources
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An effective phosphine-catalyzed protocol has been established for the syntheses of 1,3-diketones and nitriles from alkynones with oximes as hydroxide surrogates. This method features the use of a phosphine catalyst, compatibility with various functional groups and ambient temperature, which makes this approach very practical. A plausible mechanism was proposed.
- Chen, Pei,Zhang, Qian-Qian,Guo, Jia,Chen, Lu-Lu,Wang, Yan-Bo,Zhang, Xiao
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p. 6958 - 6966
(2018/10/02)
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- Regio- and Stereoselective Hydrosulfonylation of Electron-Deficient Alkynes: Access to Both E- and Z-β-Sulfonyl-α,β-Unsaturated Carbonyl Compounds
-
A metal-free hydrosulfonylation of electron-deficient alkynes with sodium sulfinates or sulfinic acids to access both E- and Z-β-sulfonyl-α,β-unsaturated carbonyl compounds has been developed. We propose that this reaction via a hydroxylallene intermediate delivers the thermodynamically stable E isomer, or via a concerted termolecular AdE3 mechanism affords Z isomer. The stereoselectivity of addition (syn or anti) can be controlled by varying the sulfonyl sources and acidic buffer solutions. This protocol exhibits broad substrate scope for internal or terminal alkynes including various substituted ynones and alkynyl esters. This approach is mild, efficient, operationally simple and easy to be scaled-up. (Figure presented.).
- Zhang, Wei,Johnson, Gabriel M.,Guan, Zhi,He, Yan-Hong
-
supporting information
p. 4562 - 4570
(2018/10/24)
-
- Synthesis of Water-Soluble Blue-Emissive Tricyclic 2-Aminopyridinium Salts by Three-Component Coupling-(3+3)-Anellation
-
The (3+3) anellation of alkynones and cyclic amidines is a novel and unexpected approach to generate intensively blue luminescent tricyclic 2-aminopyridinium salts with quantum yields Φf up to 63 % in water. By implementation into a consecutive three-component reaction, these title compounds are obtained rapidly and efficiently in a diversity-oriented fashion. Most interestingly, these bi- and tricyclic 2-aminopyridinium salts emit in dichloromethane and water solutions, thus making them interesting novel luminophore probes for bioanalytics, as well as in the solid state, thus making them blue emitters with tunable efficiency.
- Bakulina, Olga,Merkt, Franziska K.,Knedel, Tim-Oliver,Janiak, Christoph,Müller, Thomas J. J.
-
supporting information
p. 17240 - 17244
(2018/12/05)
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- Carbonylative Sonogashira Coupling of Aryl Iodides with Terminal Alkynes Catalyzed by Palladium Nanoparticles
-
A convenient and efficient method for the synthesis of α,β-alkynyl ketones from the three-component coupling of aryl iodides, terminal alkynes, and carbon monoxide (carbonylative Sonogashira coupling reaction) is successfully developed. The carbonylative Sonogashira coupling reaction proceeded smoothly under mild conditions in the presence of palladium nanoparticles to produce the corresponding α,β-alkynyl ketones in good to excellent yields.
- Feng, Xiujuan,Song, Jiliang,Bao, Ming
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p. 337 - 345
(2017/11/27)
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- Alkynylation of Csp2 (O)–H Bonds Enabled by Photoredox-Mediated Hydrogen-Atom Transfer
-
The development of new hydrogen-atom transfer (HAT) strategies within the framework of photoredox catalysis is highly appealing for its power to activate a desired C?H bond in the substrate leading to its selective functionalization. Reported here is the first photoredox-mediated hydrogen-atom transfer method for the efficient synthesis of ynones, ynamides, and ynoates with high regio- and chemoselectivity by direct functionalization of Csp2 (O)?H bonds. The broad synthetic application of this method has been demonstrated by the selective functionalization of C(O)?H bonds within complex molecular scaffolds.
- Mukherjee, Satobhisha,Garza-Sanchez, R. Aleyda,Tlahuext-Aca, Adrian,Glorius, Frank
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p. 14723 - 14726
(2017/10/18)
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- Spiroannulation of Oxindoles via Aryne and Alkyne Incorporation: Substituent-Diverted, Transition-Metal-Free, One-Pot Access to Spirooxindoles
-
A "product control via substrate design" strategy has been conceptualized and implemented to harness the potential of aryne and activated alkyne insertions into oxindoles to readily and efficiently furnish pharmacophoric indano- and cyclopentannulated spirooxindole scaffolds in an operationally straightforward, one-pot, transition-metal-free protocol.
- Samineni, Ramesh,Madapa, Jaipal,Srihari, Pabbaraja,Mehta, Goverdhan
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supporting information
p. 3119 - 3122
(2017/06/23)
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- A phosphine-free, atom-efficient cross-coupling reaction of triorganoindiums with acyl chlorides catalyzed by immobilization of palladium(0) in MCM-41
-
The first phosphine-free heterogeneous palladium(0)-catalyzed cross-coupling of triorganoindiums with acyl chlorides has been developed that proceeds smoothly in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable aryl ketones and α,β-acetylenic ketones with high atom-economy and high yield. This phosphine-free heterogeneous palladium(0) catalyst can be easily prepared from commercially available reagents and recovered by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
- Miao, Jiankang,Huang, Bin,Liu, Haiyi,Cai, Mingzhong
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p. 42570 - 42578
(2017/09/11)
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- A highly efficient heterogeneous palladium-catalyzed cascade three-component reaction of acid chlorides, terminal alkynes and hydrazines leading to pyrazoles
-
In the presence of 0.5 mol% of 3-(2-aminoethylamino)propyl-functionalized MCM-41-immobilized palladium(II) complex [MCM-41-2N-Pd(OAc)2] and 1.0 mol% of CuI, acid chlorides were coupled with terminal alkynes in Et3N at 50 °C to give α,β-unsaturated ynones, which were converted in situ into pyrazoles by the cycloaddition of hydrazines at room temperature with acetonitrile as cosolvent. The cascade reactions generated a variety of pyrazole derivatives in moderate to good yields, and this heterogeneous palladium catalyst exhibited higher catalytic activity than PdCl2(PPh3)2 and could be recovered and reused for at least 10 consecutive trials without any decreases in activity.
- Chen, Qiurong,Yao, Fang,Yin, Lin,Cai, Mingzhong
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p. 108 - 113
(2016/01/15)
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- Consecutive three- and four-component coupling-Bagley-Bohlmann-Rahtz syntheses of tri- and tetrasubstituted pyridines
-
The concatenation of the modified Sonogashira alkynone synthesis and the Bagley-Bohlmann-Rahtz pyridine synthesis gives novel consecutive three- and four-component coupling-Bagley-Bohlmann-Rahtz (cBBR) syntheses of tri- and tetrasubstituted pyridines in a one-pot fashion. With these processes 15 differently substituted 3-ethoxycarbonyl 2-methylpyridines can be readily obtained in modest to moderate yields.
- Dohe, Janis,Müller, Thomas J. J.
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p. 705 - 718
(2016/07/06)
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- Iodine/Copper Iodide-Mediated C-H Functionalization: Synthesis of Imidazo[1,2-a]pyridines and Indoles from N-Aryl Enamines
-
A practical intramolecular C-H functionalization reaction of N-aryl enamines has been carried out with molecular iodine (I2) as the sole oxidant in the presence of copper iodide (CuI). The efficient and versatile synthetic method described here
- Liu, Jing,Wei, Wei,Zhao, Ting,Liu, Xuanyu,Wu, Jie,Yu, Wenquan,Chang, Junbiao
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p. 9326 - 9336
(2016/10/14)
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- Synthesis of Iron Oxide Palladium Nanoparticles and Their Catalytic Applications for Direct Coupling of Acyl Chlorides with Alkynes
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A new, magnetic, silica-based, palladium nanocatalyst has been synthesized and employed for the first time in the direct coupling of acyl chlorides with terminal alkynes to prepare a variety of ynones. The synthesized nanocomposite is an excellent heterog
- Sharma, Rakesh K.,Yadav, Manavi,Gaur, Rashmi,Gupta, Radhika,Adholeya, Alok,Gawande, Manoj B.
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p. 1312 - 1319
(2016/12/09)
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- Carboxylic acid [...]end alkyne couplingacetylenic ketone the method of preparation
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The invention discloses a method for preparing acetyenic ketone by coupling carboxylate triazinyl ester with terminal alkyne. According to the method, palladium acetate is taken as a catalyst, and a carboxylate triazinyl ester compound is taken as an elec
- -
-
Paragraph 0014-0017; 0137
(2016/11/21)
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- Ionic palladium complex as an efficient and recyclable catalyst for the carbonylative Sonogashira reaction
-
The neutral palladium(II) complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-imidazolyl] dichloropalladium(II) (1A) ligated by thiazolylimidazolyl-based phosphine (L1) in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature, and the ionic complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-3-methylimidazolium] dichloropalladium(II) trifluoromethanesulfonate (2A) ligated by thiazolylimidazolium-based phosphine (L2) after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized. It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex, but also lowered its catalytic performance in carbonylative Sonogashira reactions. These effects reveal the important role of the N-donor in 1A. In addition, as an ionic palladium complex, 2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.
- Yang, Da,Wang, Dongliang,Liu, Huan,Zhao, Xiaoli,Lu, Yong,Lai, Shijun,Liu, Ye
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p. 405 - 411
(2016/03/16)
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- Palladium-catalyzed Sonogashira coupling of amides: Access to ynones: Via C-N bond cleavage
-
The first palladium-catalyzed Sonogashira coupling of amides has been developed, which proceeds via a selective cleavage of the N-acylsaccharin C-N bond. Notably, the new approach employs N-acylsaccharins as coupling partners to give ynones in good to excellent yield. This protocol can be efficiently utilized in the synthesis of a broad array of ynones under low catalyst loading and Cu-free conditions.
- Cui, Ming,Wu, Hongxiang,Jian, Junsheng,Wang, Hui,Liu, Chao,Daniel, Stelck,Zeng, Zhuo
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p. 12076 - 12079
(2016/10/13)
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- Oxidative Coupling of Terminal Alkynes with Aldehydes Leading to Alkynyl Ketones by Using Indium(III) Bromide
-
An indium(III)-promoted direct acylation of terminal alkynes using aldehydes leading to ynones was developed. In contrast to the previous addition reactions of alkynes to aldehydes, which provide propargylic alcohols, the oxidative coupling proceeded exclusively to afford alkynyl ketones. The products were likely generated through an Oppenauer oxidation of the indium propargylic alkoxide species by excess amounts of aldehydes.
- Ogiwara, Yohei,Kubota, Masahito,Kurogi, Kotaro,Konakahara, Takeo,Sakai, Norio
-
supporting information
p. 18598 - 18600
(2016/01/25)
-
- Sequential palladium catalyzed coupling-cyclocondensation-coupling (C3) four-component synthesis of intensively blue luminescent biarylsubstituted pyrazoles
-
1-, 3-, and 5-Biarylsubstituted pyrazoles can be efficiently prepared by a microwave-assisted consecutive four-component synthesis based upon a sequential Pd-catalyzed coupling-condensation-coupling (C3), a one-pot sequence which concatenates S
- Deni?en, Melanie,Nordmann, Jan,Dziambor, Julian,Mayer, Bernhard,Frank, Walter,Müller, Thomas J. J.
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p. 33838 - 33854
(2015/04/27)
-
- Synthesis of 3,5-disubstituted-1H-pyrazoles from acid chlorides, alkynes, and hydrazine in the presence of silica-supported-zinc bromide
-
An efficient one-pot palladium- And copper-free procedure has been developed for a convenient synthesis of 3,5-disubstituted-1H-pyrazoles from various acid chlorides, terminal alkynes and hydrazine by a coupling reaction and cyclocondensation sequence. Acid chlorides react with terminal alkynes in the presence of silica-supported-zinc bromide to give α,β-unsaturated ynones, and in situ conversion into pyrazoles by the hydrazine cyclocondensation.
- Keivanloo, Ali,Bakherad, Mohammad,Samangooei, Shahrzad
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p. 484 - 486
(2015/11/03)
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- The thermoregulated ligand-palladium-catalyzed carbonylative Sonogashira coupling of aryl iodides with terminal alkynes in water
-
An efficient and recyclable protocol via thermoregulated phase-transfer catalysis to separate the catalyst in pure water for the carbonylative Sonogashira coupling of aryl iodides with terminal alkynes has been successfully developed using the thermoregulated ligand Ph2P(CH2CH2O)nCH3 (n ≈ 22). This method allows the synthesis of a variety of alkynones in moderate to good yields (70-91%) and the catalytic system can be recycled four times without significant loss of activity.
- Hao, Yuanping,Jiang, Jingyang,Wang, Yanhua,Jin, Zilin
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p. 608 - 611
(2015/09/01)
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- Privilege Ynone Synthesis via Palladium-Catalyzed Alkynylation of "Super-Active Esters"
-
A neat palladium-catalyzed alkynylation reaction was developed with "super-active ester" as the carbonyl electrophile, which provides a clean and efficient synthetic protocol for a broad array of ynone compounds under CO-, Cu-, ligand-, and base-free conditions. The superior activity of triazine ester was rationalized by the strong electron-withdrawing ability and the unique affinity of triazine on palladium. A mechanistic experiment clearly demonstrated that the N-Pd coordination of triazine plays a crucial role for the highly efficient C-O activation. (Chemical Equation presented).
- Yu, Bo,Sun, Huaming,Xie, Zunyuan,Zhang, Guofang,Xu, Li-Wen,Zhang, Weiqiang,Gao, Ziwei
-
supporting information
p. 3298 - 3301
(2015/07/15)
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- Phosphane-ligated ionic palladium complexes: Synthesis, characterization and application as efficient and reusable precatalysts for the homogeneous carbonylative sonogashira reaction under CuI-free conditions
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The stable ionic PdII complexes 1A-4A were synthesized through the complexation of PdCl2(MeCN)2 with the phosphane-functionalized ionic liquids (FILs) 1-4 with π-acceptor character. Single-crystal X-ray diffraction analyses showed that 1A-4A were all composed of PdII-centred square-planar cations and triflate (OTf-, CF3SO3-) counteranions. The complex cations in 1A-3A possessed structural similarity to trans-PdCl2(PPh 3)2. The cation in 4A was a new PdII-centered planar complex ligated by the phosphane-carbon anion-carbene (PCC) pincer in a tripodal manner. The stabilities of 1A-4A were improved due to the intensive π-backbonding interaction between the Pd and P atoms. When complexes 1A-4A were used as precatalysts for homogeneous carbonylative Sonogashira coupling of PhI with phenylacetylene free of CuI, 1A-3A exhibited excellent catalytic behaviour with a TON of up to 1700 at a CO pressure of 0.5 MPa and moderate temperature of 100 °C, whereas 4A exhibited poor activity towards the transformation of PhI due to the high stability of 4A. The recycling experiments of 3A in [Bpy]BF4 (as a solvent) indicated that 3A could be recycled for 5 runs with neither activity loss nor metal leaching into the organic phase. Complex 3A also proved to be a general precatalyst for the carbonylative Sonogashira couplings of a wide range of aryl iodides with phenylacetylene. The selectivity of the desired carbonylation product depended more on electronic effects than the steric effects of the substituents of the aryl iodides. The ionic palladium complexes 1A-4A ligated by imidazolium-based-phosphanes were prepared and shown, by single-crystal X-ray diffraction analyses, to be composed of PdII-centered square-planar cations and OTf- counteranions. The complexes were tested as precatalysts for the homogeneous carbonylative Sonogashira coupling of aryl iodides with phenylacetylene. Copyright
- Zhang, Jing,Wang, Yongyong,Zhao, Xiaoli,Liu, Ye
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p. 975 - 985
(2014/03/21)
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- Preparation of 3,5-disubstituted pyrazoles and isoxazoles from terminal alkynes, aldehydes, hydrazines, and hydroxylamine
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The reaction of terminal alkynes with n-BuLi, and then with aldehydes, followed by the treatment with molecular iodine, and subsequently hydrazines or hydroxylamine provided the corresponding 3,5-disubstituted pyrazoles or isoxazoles in good yields with high regioselectivity, through the formations of propargyl secondary alkoxides and α-alkynyl ketones. The present reactions are one-pot preparation of 3,5-disubstituted pyrazoles from terminal alkynes, aldehydes, molecular iodine, and hydrazines, and 3,5-disubstituted isoxazoles from terminal alkynes, aldehydes, molecular iodine, and hydroxylamine.
- Harigae, Ryo,Moriyama, Katsuhiko,Togo, Hideo
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p. 2049 - 2058
(2014/04/03)
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- Oxidation of alcohols to carbonyl compounds with molecular iodine in the presence of potassium tert-butoxide
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An efficient protocol for the oxidation of alcohols to carbonyl compounds with molecular iodine and potassium tert-butoxide is described. Various primary and secondary alcohols were converted to the corresponding aldehydes and ketones in high yields. The oxidation of 2-phenylethanol produced an "abnormal" acetalic ketone. The readily availability of starting materials, convenient synthetic procedure, operational simplicity, mild reaction conditions, and high yields makes this protocol a competitive alternative in the synthesis of ynones and ketones as well as aryl aldehydes.
- Luo, Qun-Li,Nan, Wen-Hui,Li, Yu,Chen, Xiang
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p. 350 - 361
(2014/07/07)
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- Palladium- and solvent-free synthesis of ynones by copper(I)-catalyzed acylation of terminal alkynes with acyl chlorides under aerobic conditions
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Air-stable CuI/cryptand-22 complex was found to be a highly active catalyst for the solvent-free cross-coupling reaction of terminal alkynes with different acyl chlorides in the presence of Et3N as base to give the corresponding ynon
- Mohammadi, Elmira,Movassagh, Barahman,Navidi, Mozhgan
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- One-pot three-component synthesis of 3,5-disubstituted isoxazoles by a coupling-cyclocondensation sequence
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A convenient one-pot procedure for the synthesis of 3,5-disubstituted isoxazoles from acid chloride, terminal alkyne, and hydroxylamine hydrochloride catalyzed by Pd(PPh3)2Cl2/CuI has been developed. The coupling of acid c
- Liu, Hai-Ling,Geng, Zhu-Feng,Zhang, Si-Yu,Han, Jie
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p. 1221 - 1227
(2014/05/20)
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- Carbonylative Sonogashira coupling of terminal alkynes with aryl iodides under atmospheric pressure of CO using Pd(II)@MOF as the catalyst
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A novel, highly efficient, and phosphine-free heterogeneous palladium-MOF catalytic system for the carbonylative Sonogashira coupling of terminal alkynes with aryl iodides was developed. The catalyst could efficiently promote the carbonylative coupling reaction under atmospheric pressure of CO, affording the corresponding aryl α,β-alkynyl ketones in good to excellent yields. Besides high activity and selectivity, the proposed catalytic system features a broad substrate scope for both alkynes and aryl iodides. Moreover, the heterogeneous catalyst was recyclable, showed negligible metal leaching, and could be reused at least five times without significant loss in catalytic efficiency under the investigated conditions. the Partner Organisations 2014.
- Bai, Cuihua,Jian, Siping,Yao, Xianfang,Li, Yingwei
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p. 3261 - 3267
(2014/08/18)
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- Recyclable and reusable PdCl2(PPh3) 2/PEG-2000/H2O system for the carbonylative Sonogashira coupling reaction of aryl iodides with alkynes
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PdCl2(PPh3)2 in a mixture of water and poly(ethylene glycol) (PEG-2000) is shown to be an extremely active catalyst for the carbonylative Sonogashira coupling reaction of aryl iodides with terminal alkynes. The reaction can be conducted under an atmospheric pressure of carbon monoxide at 25 °C with Et3N as a base, yielding a variety of alkynyl ketones in good to excellent yields. Application of this synthetic method to prepare flavones from o-iodophenol and terminal alkynes was also achieved. The isolation of the products is readily achieved by extraction with diethyl ether, and the PdCl2(PPh3)2/PEG-2000/ H2O system can be easily recycled and reused six times without any loss of catalytic activity. the Partner Organisations 2014.
- Zhao, Hong,Cheng, Mingzhu,Zhang, Jiatao,Cai, Mingzhong
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supporting information
p. 2515 - 2522
(2014/05/06)
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- Phosphane-ligated ionic palladium complexes: Synthesis, characterization and application as efficient and reusable precatalysts for the homogeneous carbonylative sonogashira reaction under CuI-free conditions
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The stable ionic PdII complexes 1A-4A were synthesized through the complexation of PdCl2(MeCN)2 with the phosphane-functionalized ionic liquids (FILs) 1-4 with π-acceptor character. Single-crystal X-ray diffraction analyses showed that 1A-4A were all composed of PdII-centred square-planar cations and triflate (OTf-, CF3SO3-) counteranions. The complex cations in 1A-3A possessed structural similarity to trans-PdCl2(PPh3)2. The cation in 4A was a new PdII-centered planar complex ligated by the phosphane-carbon anion-carbene (PCC) pincer in a tripodal manner. The stabilities of 1A-4A were improved due to the intensive π-backbonding interaction between the Pd and P atoms. When complexes 1A-4A were used as precatalysts for homogeneous carbonylative Sonogashira coupling of PhI with phenylacetylene free of CuI, 1A-3A exhibited excellent catalytic behaviour with a TON of up to 1700 at a CO pressure of 0.5 MPa and moderate temperature of 100 °C, whereas 4A exhibited poor activity towards the transformation of PhI due to the high stability of 4A. The recycling experiments of 3A in [Bpy]BF4 (as a solvent) indicated that 3A could be recycled for 5 runs with neither activity loss nor metal leaching into the organic phase. Complex 3A also proved to be a general precatalyst for the carbonylative Sonogashira couplings of a wide range of aryl iodides with phenylacetylene. The selectivity of the desired carbonylation product depended more on electronic effects than the steric effects of the substituents of the aryl iodides.
- Zhang, Jing,Wang, Yongyong,Zhao, Xiaoli,Liu, Ye
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p. 975 - 985
(2015/04/27)
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- Addition of terminal alkynes to aromatic nitriles catalyzed by divalent lanthanide amides supported by amidates: Synthesis of ynones
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An efficient protocol has been established for the synthesis of conjugated ynones via addition of terminal alkynes to aromatic nitriles, which is catalyzed by novel divalent lanthanide amide complexes. All the reactions gave the products in good to excell
- Ding, Hao,Lu, Chengrong,Hu, Xiaolin,Zhao, Bei,Wu, Bing,Yao, Yingming
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supporting information
p. 1269 - 1274
(2013/07/11)
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- Simple and general procedure for the synthesis of α,β-alkynyl ketones from nitriles using alkynyldimethylaluminum reagents
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A simple and efficient approach for the synthesis of α,β-alkynyl ketones from nitriles and alkynyldimethylaluminum reagents, derived from trimethylaluminum and alkynes, is described. This methodology provides access to a wide range of α,β-alkynyl ketones with aliphatic, aromatic, and heteroaromatic substituents in moderate to high yield (53-90%). In the cases of aryl-substituted nitriles, the product can also be obtained as α,β-alkynyl N-H ket-imines in high yield (88-93%). Georg Thieme Verlag Stuttgart, New York.
- Korbad, Balaji L.,Lee, Sang-Hyeup
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supporting information
p. 1953 - 1958
(2013/09/24)
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- Silica gel-supported palladium catalyst for the acyl sonogashira reaction
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The acyl Sonogashira reaction between acyl chlorides and terminal alkynes is one of the most useful method for the preparation of ynones which are important intermediates to prepare versatile pharmaceutically and biologically active heterocyclic compounds such as pyrroles, pyrazoles, furans, furanones, isoxazoles, pyrimidines, quinolines, indolizidinones. 3- Mercaptopropyltrimethoxysilane and palladium supported silica has received considerable attention in organic synthesis for its availability, low cost, excellent heterogeneous nature, and ease of handling. It was effectively used in various organic syntheses. Despite various coupling reactions and exceptional heterogeneity, till now thiol containing palladium silica catalyst for ynones synthesis has not been reported. Due to the higher uptake capacity of palladium acetate in mercaptopropyl silica gel, 0.40 mmol/gm palladium loading was achieved easily. Inductively coupled plasma (ICP) analysis also confirmed the palladium content.
- Hossain, Shahin,Park, Ji-Hoon,Park, Min-Kyu,Jin, Myung-Jong
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p. 411 - 415
(2013/07/26)
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- Palladium chloride-cryptand-22 complex: An efficient catalyst for the copper-, phosphorus-, and solvent-free synthesis of ynones
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The palladium chloride-cryptand-22 complex was found to be an efficient catalyst for the copper-, phosphorus-, and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base, at room temperatu
- Navidi, Mozhgan,Movassagh, Barahman
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p. 1363 - 1367
(2013/10/01)
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