- Synthesis of acetylenic ketones by a Pd-catalyzed carbonylative three-component coupling reaction in [bmim]PF6
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A carbonylative three-component coupling reaction of aryl iodides with terminal alkynes catalyzed by PdCl2(PPh3)2 was carried out using an ionic liquid, [bmim]PF6, as the reaction medium, which resulted in good yields of α,β-acetylenic ketones. The low-viscosity ionic liquid, [bmim]NTf2, was not suitable for this reaction, since the background Sonogashira coupling reaction, a competing reaction, also proceeded.
- Fukuyama, Takahide,Yamaura, Ryo,Ryu, Ilhyong
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Read Online
- Using Pd-salen complex as an efficient catalyst for the copper- and solvent-free coupling of acyl chlorides with terminal alkynes under aerobic conditions
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The palladium-salen complex palladium(II) N,N′-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-1,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acy
- Bakherad, Mohammad,Amin, Amir Hossein,Keivanloo, Ali,Bahramian, Bahram,Raessi, Mersad
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- Carbonylative Sonogashira coupling of terminal alkynes with aqueous ammonia
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(Matrix presented) Carbonylative coupling of phenylethyne with 4-methoxy-1-iodobenzene in the presence of 1 mol% PdCl2(PPh 3)2, 2 equiv of 0.5 M aqueous ammonia, and CO (1 atm) gives the corresponding α,β-alkynyl ketone in
- Mohamed Ahmed, Mohamed S.,Mori, Atsunori
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- Direct alkynyl group transfer from silicon to copper: New preparation method of alkynylcopper (I) reagents
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A first observation of the direct alkynyl group transfer from silicon to copper is reported. The silicon group of alkynylsilanes was smoothly replaced by copper (I) chloride in DMI to give the corresponding copper (I) acetylides. This transformation was a
- Ito, Hajime,Arimoto, Kikuo,Sensui, Hiro-Omi,Hosomi, Akira
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- Palladium nanoparticles supported on Smopex metal scavengers as catalyst for carbonylative Sonogashira reactions: Synthesis of α,β-alkynyl ketones
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Palladium nanoparticles supported on two Smopex commercial metal scavengers (1% w/w) have been tested in the carbonylative Sonogashira reactions of aryl iodides with phenylacetylene. Their catalytic activity has been compared with those of more common catalysts (Pd/C, Pd/γ-Al 2O3). Pd/Smopex-234 resulted especially effective in the synthesis of alkynyl ketones even working with a low amount of palladium (0.2-0.5 mol%). Preliminary heterogeneity tests (i.e. hot filtration test, Pd leaching and recycle of the catalyst) have been performed in order to evaluate the catalytic behaviour of this system. The obtained results seem to indicate that Pd/Smopex-234 could act as a truly heterogeneous catalyst.
- Aronica, Laura Antonella,Caporusso, Anna Maria,Tuci, Giulia,Evangelisti, Claudio,Manzoli, Maela,Botavina, Maria,Martra, Gianmario
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- Organoborane-catalyzed selective 1,2-reduction of alkynones with hydride transfer: Synthesis of benzyl alkynes
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Benzyl alkynes are important organic building blocks in organic synthesis. We report herein a B(C6F5)3-catalyzed site-selective 1,2-reduction of readily available alkynones to access benzyl alkyne derivatives. Under the de
- Zhai, Lele,Yang, Zhigang,Man, Qinghong,Yang, Mingyu,Ren, Yangqing,Wang, Lei,Li, Huilin,She, Xuegong
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- Atom-Economic Synthesis of Highly Functionalized Bridged Ring Systems Initiated by Ring Expansion of Indene-1,3-dione
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An atom economic procedure for the regioselective synthesis of bridged seven-membered-ring compounds from simple reactants such as ynones and indene-1,3-dione has been developed. This process was realized through the one-pot reactions of ring-expansion of
- Mu, Yuanyang,Yao, Qiyi,Yin, Liqiang,Fu, Siyi,Wang, Mengdan,Yuan, Yang,Kong, Lingkai,Li, Yanzhong
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p. 6755 - 6764
(2021/05/06)
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- Straightforward Stereoselective Synthesis of Seven-Membered Oxa-Bridged Rings through in Situ Generated Cycloheptenol Derivatives
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An iodine-mediated stereoselective synthesis of seven-membered oxa-bridged rings via in situ generated cycloheptenols was reported. This process was realized through the combination of C-C σ-bond cleavage and C-O bond-forming reactions in a one-pot fashion from simple and easily accessible raw materials. The formation of carbon radicals initiated by I2 was the key to the reaction.
- Wang, Mengdan,Yin, Liqiang,Cheng, Lu,Yang, Yajie,Li, Yanzhong
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p. 12956 - 12963
(2021/09/13)
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- Nickel (II) dibenzotetramethyltetraaza[14]annulene supported on DFNS nanoparticles catalyst in carbonylative sonogashira coupling
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In this study, the carbonylative sonogashira coupling reaction was performed in the presence of CO (2 MPa) and Nitmtaa?DFNS as NPs. Nickel(II)dibenzotetramethyltetraaza[14]annulene complex (Nitmtaa) prepared and immobilized on amino-fucntionnalized DFNS (N-DFNS) via Ni[sbnd]N (NH2) bond to obtain a stable and reusable new nanocatalyst named as Nitmtaa?DFNS. Good to superb performance products were provided deploying Nitmtaa?DFNS nanocatalyst. In addition, the anatomy of Nitmtaa?DFNS has been distinguished by various methods, including XRD, VSM, FT-IR, SEM, EDX, TEM, and TGA. In addition, the hot filtration test provided complete insight into the heterogeneity of the catalyst. The reuse and recycling of the catalyst were repeatedly investigated for coupling reactions. In addition, the mechanism of the coupling reactions was thoroughly studied.
- Mohsen Sadeghzadeh, Seyed,Tian, Shaopeng,Yang, Qianqian
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- Sc(OTf)3-catalyzed [3 + 2]-cycloaddition of nitrones with ynones
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An efficient approach to access functionalized (2,3-dihydroisoxazol-4-yl) ketones has been developed by reacting nitrones 4 with ynones 7 or terminal ynones 10 in a one-pot fashion. The reaction went through a formal Sc(OTf)3-catalyzed [3 + 2]-cycloaddition process to generate a number of functionalized (2,3-dihydroisoxazol-4-yl) ketones 11aa-11aw, 11ba-11la and 12aa-12ae in moderate to good yields. This journal is
- He, Chun-Ting,Han, Xiao-Li,Zhang, Yan-Xue,Du, Zhen-Ting,Si, Chang-Mei,Wei, Bang-Guo
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supporting information
p. 457 - 466
(2021/01/29)
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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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- Synthesis of 2-isoxazolyl-2,3-dihydrobenzofuransviapalladium-catalyzed cascade cyclization of alkenyl ethers
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A novel palladium-catalyzed cascade cyclization reaction of alkenyl ethers with alkynyl oxime ethers for the construction of poly-heterocyclic scaffolds has been developed, in which the electron-rich alkene moiety functions as a three-atom unit, simultaneously dealing well with the coordination and regioselectivity of electron-rich olefins under metal catalysis. The strategy features excellent regio- and chemoselectivities as well as good functional group tolerance. Moreover, the newly formed 2-isoxazolyl-2,3-dihydrobenzofuran products can be further transformed to diverse complex heterocycles, demonstrating their potential applications in organic synthesis and medicinal chemistry.
- Zhou, Fei,Li, Can,Li, Meng,Jin, Yangbin,Jiang, Huanfeng,Zhang, Yingjun,Wu, Wanqing
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supporting information
p. 4799 - 4802
(2021/05/25)
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- Methylation Alkynylation of Terminal Alkenes via 1,2-Alkynyl Migration Using Dicumyl Peroxide as the Methyl Source
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The metal-free oxidative alkene methylation/alkynylation of 1,4-enyn-3-ols with an organic peroxide as the methyl source has been developed, which provides straightforward and practical access to the challenging quaternary-carbon-containing but-3-yn-1-one
- Qin, Yi-Qun,Chen, De,Liu, Liang,Zhang, Jia-Jia,Peng, Xin-Ju,Luo, Yong-Yue,Deng, Wei,Xiang, Jiannan
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p. 4700 - 4708
(2021/08/31)
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- Selective Thiocyanation and Aromatic Amination to Achieve Organized Annulation of Enaminone with Thiocyanate
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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
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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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- Electrochemical Palladium-Catalyzed Oxidative Sonogashira Carbonylation of Arylhydrazines and Alkynes to Ynones
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Oxidative carbonylation using carbon monoxide has evolved as an attractive tool to valuable carbonyl-containing compounds, while mixing CO with a stoichiometric amount of a chemical oxidant especially oxygen is hazardous and limits its application in scale-up synthesis. By employing anodic oxidation, we developed an electrochemical palladium-catalyzed oxidative carbonylation of arylhydrazines with alkynes, which is regarded as an alternative supplement of the carbonylative Sonogashira reaction. Combining an undivided cell with constant current mode, oxygen-free conditions avoids the explosion hazard of CO. A diversity of ynones are efficiently obtained using accessible arylhydrazines and alkynes under copper-free conditions. A possible mechanism of the electrochemical Pd(0)/Pd(II) cycle is rationalized based upon cyclic voltammetry, kinetic studies, and intermediates experiments.
- Cao, Yue,Hu, Jingcheng,Lei, Aiwen,Li, Haoran,Shi, Renyi,Wu, Yong,Xu, Minghao,Yi, Hong,Zeng, Li
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supporting information
p. 12460 - 12466
(2021/08/24)
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- 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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supporting information
p. 4960 - 4965
(2021/07/20)
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- One-Pot Palladium-Catalyzed Carbonylative Sonogashira Coupling using Carbon Dioxide as Carbonyl Source
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Carbonylation coupling reaction has emerged as a powerful and versatile strategy for the construction of carbonyl-containing compounds in modern synthetic chemistry over the past years. Carbon dioxide, a renewable one carbon molecule, has become one of the most attractive and promising alternative carbonyl sources due to its highly abundance, nontoxicity and stability in comparison with CO in recent years. However, in most cases, a two-chamber technique was generally necessary to allow the CO-producing and CO-consuming processes to perform successfully because of the complexities and incompatibility of reaction conditions, when carbon dioxide was utilized as carbonyl source. Herein, a practical one-pot protocol using carbon dioxide as the carbonyl source for the palladium-catalyzed carbonylative Sonogashira coupling has been established, providing an expedient and practical route to a wide range of functionalized alkynones and indoxyls under mild reaction conditions. By finding a suitable catalytic system, the method allowed the CO-generating and CO-consuming processes to proceed in one pot, wherein carbon monoxide was generated in situ from the reduction of carbon dioxide in the absence of any fluoride reagents. Simple and safe operation, readily available substrates, good functional group tolerance and mild reaction conditions are the features of the method.
- Xiong, Wenfang,Wu, Bowen,Zhu, Baiyao,Tan, Xiaobin,Wang, Lu,Wu, Wanqing,Qi, Chaorong,Jiang, Huanfeng
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p. 2843 - 2851
(2021/05/10)
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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
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supporting information
p. 2015 - 2025
(2020/05/13)
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- Selective Insertion of Alkynes into C-C σ Bonds of Indolin-2-ones: Transition-Metal-Free Ring Expansion Reactions to Seven-Membered-Ring Benzolactams or Chromone Derivatives
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An unprecedented ring expansion reaction of indolin-2-ones with alkynyl ketones under transition-metal-free conditions has been developed. Base-promoted selective cleavage of a C-C σ bond of the amide is the key in this process, which provides a straightf
- Wang, Mengdan,Yang, Yajie,Song, Bo,Yin, Liqiang,Yan, Shuhui,Li, Yanzhong
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supporting information
p. 155 - 159
(2020/01/03)
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- Reduced graphene oxide supported copper oxide nanocomposites: An efficient heterogeneous and reusable catalyst for the synthesis of ynones, 1,3-diynes and 1,5-benzodiazepines in one-pot under sustainable reaction conditions
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A greener and efficient method for the synthesis of ynones and 1,3-diynes using copper oxide nanoparticles (CuONPs) doped reduced graphene oxide (CuO@rGO) catalyst under palladium, ligand and solvent free conditions have been developed. The catalyst was s
- Sarkar, Rajib,Gupta, Ajay,Jamatia, Ramen,Pal, Amarta Kumar
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- Visible-light-mediated photocatalytic cross-coupling of acetenyl ketones with benzyl trifluoroborate
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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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- Synthesis and Characterization of Ag@g?C3N4 and Its Photocatalytic Evolution in Visible Light Driven Synthesis Of Ynone
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The primary aim of this work is to synthesize photocatalyst to promote the synthesis of ynones. In this context, we synthesized AgNPs@g?C3N4 nanocomposite. The nanocomposite was characterized by using SEM, HR-TEM, XRD, EDS, ICP-AES,
- Patel, Sunil B.,Vasava, Dilip V.
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p. 631 - 641
(2019/12/03)
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- Palladium-Catalyzed Oxidative C≡C Triple Bond Cleavage of 2-Alkynyl Carbonyl Compounds Toward 1,2-Dicarbonyl Compounds?
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A new, general palladium-catalyzed oxidative strategy for the cleavage of the C≡C triple bond is presented. By employing PdCl2, CuBr2, TEMPO and air as the catalytic system and H2O as the carbonyl oxygen atom source, a wide range of 2-alkynyl carbonyl compounds, including 1,3-disubstituted prop-2-yn-1-ones, propiolamides and propiolates, lost an alkynyl carbon to access various 1,2-dicarbonyl compounds, e.g., 1,2-diones, 2-keto amides and 2-keto esters, through Wacker oxidation, intramolecular cyclization and C—C bond cleavage cascades.
- Hu, Ming,Li, Jin-Heng,Luo, Mu-Jia,Zhou, Ming-Bo
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supporting information
p. 553 - 558
(2020/04/20)
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- Palladium-catalyzed carbonylative Sonogashira cross-coupling for the synthesis of alkynones with formic acid as the CO source
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Abstract: A practical and efficient palladium-catalyzed carbonylative Sonogashira cross-coupling reaction for the synthesis of alkynones from aryl iodides, alkynes, and formic acid as the CO source has been described. Under the assistance of PPh3/I2, formic acid can be used as the CO source for synthesis of alkynones in moderate–good yields. Furthermore, it is also successfully applied for the modification of natural products, such as vindoline and tabersonin, to obtain the corresponding products.
- Lyu, Xue,Sun, Guanglong,Zhou, Yang,Wang, Yingying,Lei, Min,Wu, Wanying,Guo, Dean
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p. 309 - 315
(2019/01/21)
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- Transition-metal-free C-C σ-bond activation of α-aryl ketones and subsequent Zn-catalyzed intramolecular cyclization: synthesis of tetrasubstituted furans
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A highly atom-economical protocol for the synthesis of tetrasubstituted furans has been developed. This process is realized through the tandem reactions of Cs2CO3 promoted C-C σ-bond activation of α-aryl ketones followed by Zn-cataly
- Yuan, Yang,Tan, Hailu,Kong, Lingkai,Zheng, Zhong,Xu, Murong,Huang, Jiaqi,Li, Yanzhong
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p. 2725 - 2733
(2019/03/12)
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- Pyrene marked benzimidazole n-heterocyclic carbene palladium metal complex and preparation and application thereof
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The invention relates to a pyrene marked benzimidazole n-heterocyclic carbene palladium metal complex. The pyrene marked benzimidazole n-heterocyclic carbene palladium metal complex is prepared from benzimidazole serving as a skeleton and pyridine serving
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Paragraph 0098; 0099; 0100; 0101; 0102
(2019/06/11)
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- Synthesis of (: Z)-β-halo α,β-unsaturated carbonyl systems via the combination of halotrimethylsilane and tetrafluoroboric acid
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A convenient and broadly applicable method for the hydrohalogenation of ynones is described, by the combination of halotrimethylsilanes and tetrafluoroboric acid. Practically, one equivalent of HX (Br?nsted acid) and BF3 (Lewis acid) is smoothly generated, which activates the carbonyl compounds. Through this protocol, 42 examples of (Z)-β-halovinyl carbonyl compounds (Cl, Br and I) were obtained, in good yields and high stereoselectivity having 2-MeTHF as a solvent.
- Da Silva, Vitor A. F.,Da Silva, Gustavo P.,Matsuo, Bianca T.,Ali, Akbar,Davis, Rebecca L.,Zukerman-Schpector, Julio,Corrêa, Arlene G.,Paix?o, Márcio W.
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supporting information
p. 519 - 526
(2019/01/24)
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- Photocatalytic Annulation-Alkynyl Migration Strategy for Multiple Functionalization of Dual Unactivated Alkenes
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A novel photoredox catalysis for multiple functionalization of two different types of unactivated alkenes in a single operation was reported through a conceptually new mode of annulation-alkynyl migration. A wide array of cyclopentane carboxylates were sy
- Zhao, Qi,Hao, Wen-Juan,Shi, Hao-Nan,Xu, Ting,Tu, Shu-Jiang,Jiang, Bo
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supporting information
p. 9784 - 9789
(2019/12/24)
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- Synthesis of 1-Cyano-3-acylnaphthalenes via Formal [4+2] Benzannulation of 2-(2-Alkynylphenyl)acetonitriles and Alkynones
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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
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p. 8090 - 8099
(2019/06/27)
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- Metal-Free Promoted CF2/CF3-Difunctionalization of Unactivated Alkenes
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An operationally simple radical difluoroalkylation/trifluoromethylation and alkynylation of unactivated alkenes under mild conditions has been developed. Through this protocol, a series of CF2/CF3- substituted linear alkynyl ketones
- Li, Ming,Zhu, Xin-Yu,Qiu, Yi-Feng,Han, Ya-Ping,Xia, Yu,Wang, Cui-Tian,Li, Xue-Song,Wei, Wan-Xu,Liang, Yong-Min
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supporting information
p. 2945 - 2950
(2019/04/27)
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- Fast and Efficient Continuous Flow Method for the Synthesis of Ynones and Pyrazoles
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In this study, we developed a convenient and efficient two-step method for the synthesis of ynones in a flow reactor, through the generation of lithium acetylide and its subsequent reactions with acid chlorides. Using this approach, we obtained the ynones in moderate to good yields at room temperature. Moreover, we transformed the ynones into pyrazole derivatives through coupling with hydrazines. This transition metal-free process, mild reaction conditions, and broad functional group tolerance are all attractive features in comparison with conventional bench-top methods.
- Kandasamy, Mohanraj,Ganesan, Balaji,Hung, Min-Yuan,Lin, Wei-Yu
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supporting information
p. 3183 - 3189
(2019/05/28)
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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
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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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- One-pot regioselective synthesis of substituted pyrazoles and isoxazoles in PEG-400/water medium by Cu-free nano-Pd catalyzed sequential acyl Sonogashira coupling-intramolecular cyclization
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Catalyst efficacy of in situ generated Pd-nanoparticles (PdNPs) in the regioselective one-pot synthesis of 3,5-di & 3,4,5-trisubstituted pyrazoles and 3,5-disubstituted isoxazoles in environmentally benign PEG-400/H2O medium, which involves the sequential (i) Cu-free acyl-Sonogashira coupling (ASC) and (ii) intramolecular ynone-amine cyclization under PTC conditions was described. The results of controlled experiments support the operation of two sequential catalytic cycles (ASC/cyclization) and achievement of complementary/opposite regioselectivity via ynone-bound palladium in a one-pot approach. Moreover, the in situ PdNPs recovered after the first catalytic cycle of the one-pot reaction sequence have been reused again five times successively. Besides, prior to the above studies, the efficacy of some common Pd-N-heterocyclic carbene (Pd-NHC) complexes in catalyzing the same one-pot two-step reaction sequence (Cu-free ASC/cyclization) both in water and organic solvents was also optimized. In situ generation of PdNPs from above Pd-NHCs in water was also identified, but they are not reusable due to their large size distribution.
- Thirukovela, Narasimha Swamy,Balaboina, Ramesh,Botla, Vinayak,Vadde, Ravinder,Jonnalagadda, Sreekantha Babu,Vasam, Chandra Sekhar
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p. 6471 - 6481
(2019/11/20)
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- Acyl Radicals from Benzothiazolines: Synthons for Alkylation, Alkenylation, and Alkynylation Reactions
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We describe herein a fundamentally new visible light-driven homolytic C-C bond breaking mode for the generation of acyl radicals from C2-acyl-substituted benzothiazolines. The reactive species can be used as versatile synthons for formal radical alkylatio
- Li, Lei,Guo, Shan,Wang, Qi,Zhu, Jin
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supporting information
p. 5462 - 5466
(2019/08/01)
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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
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supporting information
p. 7036 - 7041
(2019/08/01)
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- N-heterocyclic carbene palladium complex crystal and synthetic method thereof and application of n-heterocyclic carbene palladium complex crystal in preparation of alpha,beta-unsaturated ketone compounds
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The invention discloses an n-heterocyclic carbene palladium complex crystal and a synthetic method thereof and application of the n-heterocyclic carbene palladium complex crystal in preparation of alpha,beta-unsaturated ketone compounds. A structural form
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Paragraph 0029-0032; 0051-0054
(2019/11/28)
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- Cascade and Effective Syntheses of Functionalized Tellurophenes
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A one-pot and transition-metal-catalyst-free synthetic strategy to construct functionalized tellurophenes has been developed. Substituted 1,1-dibromo-1-en-3-ynes are smoothly converted to tellurophenes with telluride salts in high yield via a series of cascade reactions through reductive debromination, hydrotelluration, nucleophilic cyclization, and aromatization. Close inspection of the results clearly showed that the reactivity of in situ prepared telluride salts are significantly influenced by the polarity of the solvent system and the electronic nature of the substituent on the enyne substrate. This method reports the first direct synthesis of 3-aryltellurophenes in high yields at room temperature. This novel reaction strategy is also found to be a promising synthetic method for multisubstituted tellurophenes and selenophenes.
- Karapala, Vamsi Krishna,Shih, Hong-Pin,Han, Chien-Chung
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supporting information
p. 1550 - 1554
(2018/03/23)
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- Transition-Metal-Free Ring Expansion Reactions of Indene-1,3-dione: Synthesis of Functionalized Benzoannulated Seven-Membered Ring Compounds
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A novel ring expansion reaction of indene-1,3-dione with alkynyl ketones under transition-metal-free conditions has been developed. This process offers an efficient and direct way to synthesize benzoannulated seven-membered rings or fused-ring compounds t
- Yao, Qiyi,Kong, Lingkai,Wang, Mengdan,Yuan, Yang,Sun, Ruizhuo,Li, Yanzhong
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supporting information
p. 1744 - 1747
(2018/04/14)
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- Carbonylative Sonogashira Coupling of Aryl Iodides with Terminal Alkynes Catalyzed by Palladium Nanoparticles
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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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- Integration of co2 reduction with subsequent carbonylation: Towards extending chemical utilization of co2
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Currently, it still remains a challenge to amplify the spectrum of chemical fixation of CO2, although enormous progress has been achieved in this field. In view of the widespread applications of CO in a myriad of industrial carbonylation processes, an alternative strategy is proposed in which CO2 reduction to CO is combined with carbonylation with CO generated ex situ, which affords efficiently pharmaceutically and agrochemically attractive molecules. As such, CO2 in this study was efficiently reduced by triphenysilane using CsF to CO in a sealed two-chamber reactor. Subsequently, palladium-catalyzed aminocar-bonylation, carbonylative Sonogashira coupling of aryl iodides, and rhodium(I)-mediated Pauson–Khand-type reaction proceeded smoothly to yield amides, alkynones, and bicyclic cy-clopentenones, respectively. Furthermore, the formed alkynones can further be successfully converted to a series of heterocycles, for example, pyrazoles, 3a-hydroxyisoxazolo[3,2-a]isoindol-8-(3aH)-one derivatives and pyrimidines in moderate yields. The striking features of this protocol include operational simplicity, high efficiency, and relatively broad application scope, which represents an alternative avenue for CO2 transformation.
- Lang, Xian-Dong,He, Liang-Nian
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- Complementary regioselective synthesis of 3,5-disubstituted isoxazoles from ynones
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Two regioselective synthetic routes towards 3,5-disubstituted isoxazoles from ynones are reported. One route takes place via first converting the ynones to ynone O-methyl oximes, followed by a palladium-catalyzed intramolecular cyclization. The other invo
- Liu, Xiaochen,Hong, Dongsub,She, Zhigang,Hersh, William H.,Yoo, Barney,Chen, Yu
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p. 6593 - 6606
(2018/10/05)
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- An easy access towards quinazolines via an improved protocol for ynones
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A simple and convenient method has been developed to accomplish Pt/2,2'-bipyridyl catalyzed acyl Sonagashira coupling for the efficient synthesis of ynones. The reaction display significant tolerance to various functional groups and the methodology has be
- Ghosh, Subhadeep,Das, Asish R.
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p. 1249 - 1258
(2020/06/27)
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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
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supporting information
p. 3596 - 3600
(2018/06/26)
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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
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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
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supporting information
p. 4562 - 4570
(2018/10/24)
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- TfOH-Promoted Reaction of 2,4-Diaryl-1,1,1-Trifluorobut-3-yn-2-oles with Arenes: Synthesis of 1,3-diaryl-1-CF3-indenes and versatility of the reaction mechanisms
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The TfOH-mediated reactions of 2,4-diaryl-1,1,1-trifluorobut-3-yn-2-oles (CF3-substituted diaryl propargyl alcohols) with arenes in CH2Cl2 afford 1,3-diaryl-1-CF3-indenes in yields up to 84%. This new process for synthesis of such CF3-indenes is complete
- Zerov, Aleksey V.,Kazakova, Anna N.,Boyarskaya, Irina A.,Panikorovskii, Taras L.,Suslonov, Vitalii V.,Khoroshilova, Olesya V.,Vasilyev, Aleksander V.
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supporting information
(2018/11/30)
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- Cycloaddition Reaction of α,β-Alkynic Hydrazones and KSCN under Transition-Metal-Free Conditions: Synthesis of N-Iminoisothiazolium Ylides
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A novel heteroannulation reaction between α,β-alkynic hydrazones and potassium thiocyanate has been developed for the synthesis of N-iminoisothiazolium ylides. The transformation features wide substrate scope, functional tolerance, and easy operation. This investigation involves a [4 + 1]-type cycloaddition reaction and C-S/S-N bond formation under transition-metal-free conditions. The application of this transformation to the gram-scale preparation of the N-imide ylide is also accomplished.
- Liu, Bei-Bei,Cao, Wen-Bin,Wang, Fei,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 11118 - 11124
(2018/09/06)
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- A general two-step one-pot synthesis process of ynones from α-keto acids and 1-iodoalkynes
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A general two-step one-pot synthesis process of ynones was developed by cycloaddition of α-keto acids and 1-iodoalkynes followed by a ring-opening reaction. Its easy conditions and novel mechanism endowed it with two distinctive advantages: iodine-atom bonded to C(sp2) remained intact and α-keto acids became a part of the triple bonds in ynones.
- Zeng, Xiaobao,Liu, Chulong,Yang, Weiguang,Wang, Xingyong,Wang, Xinyan,Hu, Yuefei
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supporting information
p. 9517 - 9520
(2018/08/28)
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- Silver-catalyzed Double Decarboxylative Radical Alkynylation/Annulation of Arylpropiolic Acids with α-keto Acids: Access to Ynones and Flavones under Mild Conditions
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Ynones are privileged building blocks in various organic syntheses of heterocyclic derivatives due to their multifunctional nature, and flavones are an important class of natural products with a wide range of biological activities. We describe the catalytic double decarboxylative alkynylation of arylpropiolic acids with α-keto acids. With Ag(I)/persulfate as the catalysis system, the valuable ynones bearing various substituents could be easily obtained. The introduction of hydroxyl substituent on ortho-site of α-keto acids make this strategy further applicable to the construction of flavone derivatives via heteroannulation in moderate to good yields with a similar silver-catalyzed system. The reactions proceed under relatively mild reaction conditions and tolerate a wide variety of functional groups. Control experiments indicated that both the reactions undergo radical processes. (Figure presented.).
- Meng, Mengting,Wang, Guofang,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
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p. 1218 - 1231
(2018/02/16)
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- Method for preparing acetyenic ketone compound by using B-form DNA to promote Sonogashira reaction
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The invention discloses a method for preparing an acetyenic ketone compound by using B-form DNA to promote Sonogashira reaction. According to the method, the B-form DNA is used as an accelerant, purewater is used as a solvent, potassium carbonate is taken
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Paragraph 0014; 0043; 0044; 0045
(2018/09/08)
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