- Multicomponent tandem reactions and polymerizations of alkynes, carbonyl chlorides, and thiols
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Multicomponent tandem reactions (MCTRs), with multiple bonds formed in a highly concise fashion in a single vessel, have been noted as one of the most powerful and popular synthetic strategies in modern organic chemistry. Attracted by their operational simplicity, synthetic efficiency, high atom economy, and environmental benefit, the MCTRs and the corresponding multicomponent tandem polymerizations (MCTPs) of alkynes, carbonyl chlorides, and aliphatic/aromatic thiols were developed. By combining the Sonogashira coupling reaction between alkynes and carbonyl chlorides, and the hydrothiolation reaction of electron-deficient alkynone intermediates, high atom economy was achieved in such one-pot, two-step, three-component reactions/polymerizations. The MCTPs can proceed efficiently under mild conditions near room temperature to afford sulfur-rich polymers with high molecular weight, high yield, high regioselectivity, and good stereoselectivity. Through the MCTPs of different combination of monofunctional and bifunctional monomers, polymers with tunable backbone structures and photophysical properties can be obtained. These polymers generally possess good solubility and film-forming ability. Their thin films enjoy high refractivity, and their photosensitivity enables easy modulation of the thin film refractive indices.
- Zheng, Chao,Deng, Haiqin,Zhao, Zujin,Qin, Anjun,Hu, Rongrong,Tang, Ben Zhong
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Read Online
- Flexible Construction of Functionalized-Pyrroles under Palladium or Copper Catalysis in the Presence of BF3 ? Et2O
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We have developed a flexible approach enabling the access to highly functionalized pyrroles under palladium or copper catalysis in the presence of BF3 ? Et2O. This catalytic methodology utilizes commercially available amines as react
- Guo, Wusheng,Liu, Teng,Liu, Yin,Wei, Kun,Yan, Biwei
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supporting information
(2022/01/26)
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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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- Nickel-Catalyzed Decarbonylative Cycloaddition of Benzofuran-2,3-diones with Alkynes to Flavones
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Using dppe as the ligand, the Nickel-catalyzed decarbonylative cycloaddition of benzofuran-2,3-diones with alkynes was established, and a variety of functional flavones were synthesized in 65–99% yields. Terminal alkynes with substituted phenyl groups and internal alkynes such as aryl acyl acetylenes and diphenylacetylenes are suitable for this reaction. The effects of bases on the reactions of different types of alkyne substrates were also investigated and discussed. (Figure presented.).
- Zhang, Yu-Yang,Li, Han,Jiang, Xiaoding,Subba Reddy, Chitreddy V,Liang, Hao,Zhang, Yaqi,Cao, Rihui,Sun, Raymond Wai-Yin,Tse, Man Kin,Qiu, Liqin
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supporting information
p. 525 - 530
(2021/12/22)
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- Cascade Skeletal Rearrangement of Gold Carbene Intermediates: Synthesis of Medium-Sized Pyrimidine-Fused Benzolactones
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A gold-catalyzed cyclization/cascade skeletal rearrangement of o-cyanophenylalkynones with 3-amino-benzo[d]-isoxazoles has been developed, which provides an approach for synthesizing medium-sized benzolactones. Based on the experimental results, we postul
- Hu, Xiaoping,Liu, Yuanhong,Wang, Ali,Xie, Xin
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p. 3769 - 3774
(2021/07/17)
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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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- Enantioselective [3 + 2] annulation of 4-isothiocyanato pyrazolones and alkynyl ketones under organocatalysis
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An asymmetric [3 + 2] annulation reaction of 4-isothiocyanato pyrazolones with alkynyl ketones in the presence of an organic catalyst derived from a cinchona alkaloid under mild conditions is realized. This protocol provides unprecedented expeditious access to a wide range of optically active spiro[pyrroline-pyrazolones] with various electronic properties in high yields with good to excellent enantioselectivities.
- Wang, Wenyao,Wei, Shiqiang,Bao, Xiaoze,Nawaz, Shah,Qu, Jingping,Wang, Baomin
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supporting information
p. 1145 - 1154
(2021/02/16)
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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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- 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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- Direct Photoexcitation of Ethynylbenziodoxolones: An Alternative to Photocatalysis for Alkynylation Reactions**
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Ethynylbenziodoxolones (EBXs) are commonly used as radical traps in photocatalytic alkynylations. Herein, we report that aryl-substituted EBX reagents can be directly activated by visible light irradiation. They act as both oxidants and radical traps, alleviating the need for a photocatalyst in several reported EBX-mediated processes, including decarboxylative and deboronative alkynylations, the oxyalkynylation of enamides and the C?H alkynylation of THF. Furthermore, the method could be applied to the synthesis of alkynylated quaternary centers from tertiary alcohols via stable oxalate salts and from tertiary amines via aryl imines. A photocatalytic process using 4CzIPN as an organic dye was also developed for the deoxyalkynylation of oxalates.
- Amos, Stephanie G. E.,Cavalli, Diana,Le Vaillant, Franck,Waser, Jerome
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p. 23827 - 23834
(2021/09/25)
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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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- 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.
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supporting information
p. 4342 - 4349
(2020/12/25)
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- The synthesis of β-enaminones using trialkylamines and a Pd/DNA catalyst
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A new one-pot procedure leading to β-enaminones has been developed. The elaborated methodology involves the cascade sequencing of carbonylative Sonogashira coupling of aryl iodide with a terminal alkyne and the oxidative dealkylation of tertiary amines. The efficient syntheses of β-enaminones were performed with a Pd/DNA catalyst, with NEt3, NPr3 and NBu3 used as amine sources. The catalyst was successfully recovered and used in several subsequent tests with the same results. The reaction mechanism, summarizing the activity of immobilized Pd NPs (palladium nanoparticles), was proposed.
- Mart,Trzeciak
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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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- Preparation method of acetylenic ketone compound
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The invention provides a preparation method of an acetylenic ketone compound, which comprises the following step: reacting a compound with a structure as shown in a formula (II) with a compound with a structure as shown in a formula (III) under the action of a catalyst and an alkali to obtain the acetylenic ketone compound with a structure as shown in a formula (I). Compared with the prior art, the method has the advantages that the N-formyl saccharin is used as a carbon monoxide substitute reagent to realize carbonyl insertion reaction of bromo-aromatic hydrocarbon and a terminal alkyne compound under the catalysis of the palladium catalyst, so that the acetylenic ketone compound is obtained, the operation is simple, the raw materials and the reagent are easy to obtain, and the condition is mild; the method avoids the use of inflammable and explosive carbon monoxide gas and formic acid, oxalic acid and other acid corrosive carbon monoxide substitute reagents, the catalytic system is green and environment-friendly, the product is easy to separate and purify, and the high-purity acetylenic ketone compound can be efficiently prepared with a high yield.
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Paragraph 0058-0065
(2021/10/30)
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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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- Solvent switchable Pd/DNA catalyst in carbonylative Sonogashira coupling
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Palladium catalysts immobilized on DNA (Pd/DNA) were applied for the first time in the carbonylative Sonogashira coupling, at 1 atm of CO. Different alkynones were obtained with a high yield in DMF. In the presence of water, the selectivity completely changed and diaryl alkynes, typical Sonogashira products, were selectively formed. In addition to Pd/DNA, soluble palladium species also participated in the catalytic process. The stability of the catalytic system increased after the addition of DNA excess.
- Mart, M.,Trzeciak, A. M.
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- Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol with oxygen as oxidizing agent and application
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The invention discloses a copper-catalyzed method for preparing an aldehyde or ketone compound by oxidizing alcohol with oxygen as an oxidizing agent. Reaction is performed in an organic solvent for 4-48 hours at room temperature by using copper salt and nitroxide free radicals as catalysts and oxygen or air as an oxidizing agent to efficiently oxidize an alcohol compound into the corresponding aldehyde or ketone compound. The method is simple to operate, free of chlorides corrosive to equipment, available in raw materials and reagents, mild in reaction conditions, wide in substrate universality, good in functional group compatibility, convenient in separation and purification, environmentally friendly in the whole process and free of pollution, and is a method suitable for industrial production.
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Paragraph 0028-0030; 0061-0063
(2020/08/18)
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- A sustainable access to ynones through laccase/TEMPO-catalyzed metal- and halogen-free aerobic oxidation of propargylic alcohols in aqueous medium
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Tuning laccase/TEMPO-catalyzed aerobic oxidation of secondary propargylic alcohols in aqueous media was accomplished in order to efficiently synthesize ynones. This study led to the formulation of an effective and sustainable catalytic method for the preparation of mono- and bis-substituted ynones compared with traditional oxidative methods.
- Silva, Alana B.V.,Silva, Emmanuel D.,dos Santos, Alcindo A.,Princival, Jefferson L.
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- Photochemical oxidation of benzylic primary and secondary alcohols utilizing air as the oxidant
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A mild and green photochemical protocol for the oxidation of alcohols to aldehydes and ketones was developed. Utilizing thioxanthenone as the photocatalyst, molecular oxygen from air as the oxidant and cheap household lamps or sunlight as the light source, a variety of primary and secondary alcohols were converted into the corresponding aldehydes or ketones in low to excellent yields. The reaction mechanism was extensively studied.
- Nikitas, Nikolaos F.,Tzaras, Dimitrios Ioannis,Triandafillidi, Ierasia,Kokotos, Christoforos G.
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supporting information
p. 471 - 477
(2020/02/13)
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- Lewis-acid-catalyzed asymmetric alkynylation of alkynyl 1,2-diketones: Controllable formation of 3(2 H)-furanones and α-hydroxy ketones
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We report the highly regio- and enantioselective alkynylation of alkynyl 1,2-diketones under Lewis acid catalysis, leading to the formation of a series of biologically important 3(2H)-furanones with high to excellent ee values. Moreover, a slight change of the reaction conditions produces a range of highly functionalized α-hydroxy ketones with a high level of enantioselectivity. A variety of further transformations can be easily achieved, demonstrating the synthetic potential of this protocol.
- Liu, Rui,Yang, Shuang,Chen, Zhizhou,Kong, Xiangwen,Ding, Houqiang,Fang, Xinqiang
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p. 6948 - 6953
(2020/09/15)
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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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- Gold-catalyzed partial hydrogenation of activated alkynes mediated by triphenylphosphine
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Gold(I) can exhibit a cooperative effect with triphenylphosphine, accelerating the triphenylphosphine-mediated partial hydrogenation of activated alkynes. In this protocol, 3-arylpropiolates are selectively reduced to the Z -isomer when the aryl ring bears an electron-donor substituent, whereas 3-arylpropynones are reduced to the E-isomers.
- Cocoletzi-Xochitiotzi, Ana Patricia,Hernández-Hernández, Miguel,Medina-Mercado, Ignacio,Jiménez-Martínez, Williams De Jesús,Mastranzo, Virginia Maricela,Porcel, Susana
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supporting information
p. 2379 - 2386
(2020/08/19)
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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(II) on 4 ? Molecular Sieves: A Simple and Reusable Catalyst for the Preparation of Ynones
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Abstract: Pd2+ on 4?? molecular sieves support has been prepared and investigated. The catalyst has successfully been used in the reaction of acyl chlorides and terminal alkynes yielding ynones. The catalyst can be reused without significant lo
- Juhász, Kinga,Hell, Zoltán
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p. 3335 - 3341
(2020/05/13)
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- Cyclobutene Formation by Borane Catalyzed [2+2] Cycloaddition of a Vinylphosphane with Conjugated Ynones
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Dimesityl(vinyl)phosphane reacts with benzoyl(phenyl)acetylene under B(C6F5)3 catalysis to give the formal [2+2] cycloaddition product 1-benzoyl-2-phenyl-3-dimesitylphosphinocyclobutene.
- Tao, Xin,Gruber, Maurice M.,Daniliuc, Constantin G.,Mück-Lichtenfeld, Christian,Kehr, Gerald,Erker, Gerhard
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supporting information
p. 2270 - 2272
(2020/05/22)
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- Practical synthesis of α,β-Alkynyl ketones by oxidative alkynylation of aldehydes with hypervalent alkynyliodine reagents
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A practical, metal-free carbonyl C(sp2)H oxidative alkynylation of aldehydes with hypervalent alkynyliodine reagents without the use of any catalysts is described for the synthesis of various α,β-alkynyl ketones. Here, two different methods have been developed where limiting reagents or substrates can be switched, and adopted according to the valuableness of aldehyde substrates or hypervalent alkynyliodine reagents. These reactions proceed with a broad substrate scope and high functional-group compatibility.
- Tsuzuki, Saori,Sakamoto, Ryu,Maruoka, Keiji
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supporting information
p. 633 - 636
(2020/10/08)
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- Palladium/copper-cocatalyzed decarbonylative alkynylation of acyl fluorides with alkynylsilanes: Synthesis of unsymmetrical diarylethynes
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Palladium/copper-cocatalyzed decarbonylative alkynylation of acyl fluorides with alkynylsilanes is described. This reaction not only effectively inhibits the formation of undesired homocoupled products by avoiding the addition of a base, but also exhibits a wide substrate scope to provide a general access to diverse unsymmetrical diarylethynes.
- Chen, Qiang,Fu, Liyan,Nishihara, Yasushi
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supporting information
p. 7977 - 7980
(2020/09/09)
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- Ionic liquid-mediated benzoyl transfer-coupling in the Suzuki and Sonogashira reactions and aryl transfer-coupling by decarbonylative Heck reaction, using N-Benzoyl-saccharin (NBSac) as reagent
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The efficacy of N-benzoyl-saccharin (NBSac) as reagent for selective benzoyl transfer-coupling in the Suzuki reaction in BMIM-IL/[PAIM][NTf2] as solvent/base, and in the Sonogashira reaction employing guanidinium-IL (GIL) as solvent, are demonstrated. Decarbonylative aryl transfer-coupling occurs in the Heck reaction employing GIL as solvent. The reactions are catalyzed by Pd(OAc)2 or NiCl2(dppp), are performed under mild conditions in good yields, and have the potential for recycling/reuse of the IL solvent. Collectively, these methods provide facile access to diverse libraries of diarylketones, keto-ethynes and diaryl-ethenes.
- Malunavar, Shruti S.,Sutar, Suraj M.,Prabhala, Pavankumar,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
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supporting information
(2020/05/18)
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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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- Graphitic Carbon Nitride Polymer as a Recyclable Photoredox Catalyst for Decarboxylative Alkynylation of Carboxylic Acids
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Visible-light-induced heterogeneous photocatalysis for decarboxylative alkynylation has been performed. The using of cheap, metal-free and recyclable graphitic carbon nitride (g-C3N4) as the photoredox catalyst in the process enables
- Guo, Jiaqi,Wang, Yating,Li, Yuhang,Lu, Kailin,Liu, Shihui,Wang, Wei,Zhang, Yongqiang
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supporting information
p. 3898 - 3904
(2020/08/07)
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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; 0035-0038
(2019/11/28)
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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 0049; 0050; 0051; 0052; 0053; 0054; 0055-0066
(2019/06/11)
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- Method for preparing acetylene acetone compounds
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The invention discloses a method for preparing acetylene acetone compounds. The method comprises the step of subjecting a propynol compound to a reaction with acetonitrile at room temperature under the oxidation of N-iodo succinimide (NIS), thereby obtain
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Paragraph 0014
(2020/01/12)
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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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- Synthesis of benzoxazoles via the copper-catalyzed hydroamination of alkynones with 2-aminophenols
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We describe herein the synthetic method to benzoxazole derivatives via the copper-catalyzed hydroamination of alkynones with 2-aminophenols. The method produced a wide variety of functionalized benzoxazole derivatives in good yields. Preliminary mechanistic experiments revealed that the reaction would proceed through the copper-catalyzed hydroamination of alkynones and the sequential intramolecular cyclization of β-iminoketones/elimination of acetophenone promoted by the copper catalyst.
- Oshimoto, Kohei,Tsuji, Hiroaki,Kawatsura, Motoi
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supporting information
p. 4225 - 4229
(2019/05/10)
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- Synthesis and photophysical properties of 3,5-diaryl-2-heteroarylthiophenes
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A series of 3,5-diaryl-2-heteroarylthiophenes have been synthesized via Fiesselmann type reaction between alkynones and easily available heteroarylmethanethiols or heteroarylmethyl carbamimidothioates. A correlation between compounds structure and efficie
- Karpavi?ien?, Ieva,Jonu?is, Mantas,Leduskrasts, Kaspars,Misiūnait?, Indr?,Suna, Edgars,?ikotien?, Inga
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- Activating Pyrimidines by Pre-distortion for the General Synthesis of 7-Aza-indazoles from 2-Hydrazonylpyrimidines via Intramolecular Diels-Alder Reactions
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Pyrimidines are almost unreactive partners in Diels-Alder cycloadditions with alkenes and alkynes, and only reactions under drastic conditions have previously been reported. We describe how 2-hydrazonylpyrimidines, easily obtained in two steps from commercially available 2-halopyrimidines, can be exceptionally activated by trifluoroacetylation. This allows a Diels-Alder cycloaddition under very mild reaction conditions, leading to a large diversity of aza-indazoles, a ubiquitous scaffold in medicinal chemistry. This reaction is general and scalable and has an excellent functional group tolerance. A straightforward synthesis of a key intermediate of Bayer's Vericiguat illustrates the potential of this cycloaddition strategy. Quantum mechanical calculations show how the simple N-trifluoroacetylation of 2-hydrazonylpyrimidines distorts the substrate into a transition-state-like geometry that readily undergoes the intramolecular Diels-Alder cycloaddition.
- Le Fouler, Vincent,Chen, Yu,Gandon, Vincent,Bizet, Vincent,Salomé, Christophe,Fessard, Thomas,Liu, Fang,Houk,Blanchard, Nicolas
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supporting information
p. 15901 - 15909
(2019/10/22)
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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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- 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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- Emission solvatochromic, solid-state and aggregation-induced emissive α-pyrones and emission-tuneable 1H-pyridines by Michael addition–cyclocondensation sequences
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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.
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supporting information
p. 2684 - 2703
(2019/12/11)
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- Synthesis of C4-alkynylisoxazoles: Via a Pd-catalyzed Sonogashira cross-coupling reaction
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A Pd-catalyzed Sonogashira cross-coupling reaction for the synthesis of C4-alkynylisoxazoles from 3,5-disubsitituted-4-iodoisoxazoles and terminal alkynes was described, which could afford the corresponding products with high yield (up to 98%). The result
- Yang, Wen,Yao, Yongqi,Yang, Xin,Deng, Yingying,Lin, Qifu,Yang, Dingqiao
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p. 8894 - 8904
(2019/03/28)
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- Copper-Mediated Deacylative Coupling of Ynones via C-C Bond Activation under Mild Conditions
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The intermolecular deacylative coupling of unstrained ynones via C-C bond activation was accomplished by a CuCl-bpy system under mild reaction conditions. This protocol features facile cleavage of the C-C bond at room temperature, broad substrate scope, and efficient construction of important symmetric and unsymmetrical 1,3-diyne adducts through homo or cross coupling of ynones, respectively. The preliminary mechanistic investigations indicated that an acyl copper(III) complex is likely involved in this process.
- Feng, Lili,Hu, Tingjun,Zhang, Saisai,Xiong, Heng-Ying,Zhang, Guangwu
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supporting information
p. 9487 - 9492
(2019/12/02)
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- A trisulfur radical anion (S3-) involved sulfur insertion reaction of 1,3-enynes: Sulfide sources control chemoselective synthesis of 2,3,5-trisubstituted thiophenes and 3-thienyl disulfides
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Cascade cyclization reactions of S3-in situ generated from S2- with 1,3-enynes for the chemoselective synthesis of 2,3,5-trisubstituted thiophenes and 3-thienyl disulfides controlled by sulfide salts are develop
- Li, Jing-Hao,Huang, Qi,Rao, Weidong,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 7808 - 7811
(2019/07/08)
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- Synthesis of 4,5-disubstituted-1H-1,2,3-triazoles
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Abstract: Two-step procedure, a palladium catalyzed Sonogashira cross-coupling reaction of aroyl chlorides with aryl acetylenes, and 1,3-dipolar cycloaddition of the 1,3-diarylprop-2-yn-1-ones with sodium azide under catalyst free conditions achieved the
- Rocha, Djenisa H. A.,Pinto, Diana C. G. A.,Silva, Artur M. S.
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p. 1479 - 1486
(2019/07/22)
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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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- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
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Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
- Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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p. 11823 - 11838
(2019/10/02)
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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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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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p. 7036 - 7041
(2019/08/01)
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