- Waste-minimized synthesis of C2 functionalized quinolines exploiting iron-catalysed C-H activation
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Herein we present an efficient and regioselective iron-catalyzed methodology for the external oxidant-free functionalization of quinoline-N-oxides. The protocol, based on the use of inexpensive and easily accessible FeSO4, showed broad applicability to a wide range of substrates. An additional green feature of this synthetic methodology is H2O being the only by-product. Experimental and computational investigations provide support to a mechanism based on a facile C-H activation event. The green efficiency of the process has also been carefully assessed using: (i) metrics related to the synthetic process (AE, Yield, 1/SF, MRP and RME); (ii) safety/hazard metrics (SHZI and SHI); and (iii) metrics related to the metal used as the catalyst (Abundance, OEL and ADP). In addition to the many advantages of this protocol related to the green iron catalyst used and the safety/hazard features of the process, an E-factor value of ca. 0.92 (84 to >99% reduction compared to known protocols) evidently confirms the sustainable efficiency of the procedure presented. Practical utility has also been demonstrated by performing the reaction efficiently on a multi-gram scale. This journal is
- Ferlin, Francesco,Zangarelli, Agnese,Lilli, Simone,Santoro, Stefano,Vaccaro, Luigi
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supporting information
p. 490 - 495
(2021/01/28)
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- MnO2 mediated sequential oxidation/olefination of alkyl-substituted heteroarenes with alcohols
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A practical and efficient ligand-free MnO2 mediated sequential oxidation and olefination has been developed for the facile synthesis of a broad range of unsaturated N-heteroazaarenes from simple alkyl-substituted heteroarenes and alcohols. The procedure tolerates a series of functional groups, such as methoxyl, chloro, bromo, iodo, vinyl, phenolic and hetero groups, providing the olefination products in moderate to good yields.The protocol could be conducted at mild conditions and used environmentally friendly air as the clear oxidant.
- Zhang, Chunyan,Li, Zehua,Fang, Yanchen,Jiang, Shaohua,Wang, Maorong,Zhang, Guoying
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supporting information
(2020/02/15)
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- Iron/TEMPO-catalyzed direct aerobic oxidative coupling of methyl-mubstituted N-heteroazaarenes with alcohols
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A novel direct oxidative coupling of methyl-substituted N-heteroazaarenes with alcohols has been developed to construct olefins under mild condition. The reaction is catalyzed by Fe(NO3)3·9H2O/TEMPO with oxygen as terminal oxidant. A variety of E-disubstituted olefins bearing diverse functional groups could be obtained selectively in moderate to excellent yields. The reaction is environmentally friendly and ligand-free.
- Zhang, Zhiguang,Ma, Yantao,Dai, Siwei,Li, Ling,Zhang, Yong,Li, Hao
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supporting information
(2020/04/21)
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- Preparation method of trans-disubstituted olefin
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The invention relates to the technical field of organic chemical synthesis, and in particular, relates to a preparation method of trans-disubstituted olefin. According to the preparation method, primary alcohol and methyl azacycle are taken as raw materials, transition metal salt, nitric oxide and alkali are taken as catalysts, an organic solution is taken as a reaction medium, and reaction is carried out in an oxygen atmosphere. According to the preparation method, a reaction by-product is only water, the environment is not polluted, the required transition metal catalyst is cheap and easy toobtain, the reaction does not need high temperature, and the reaction cost and the requirements on reaction conditions can be reduced.
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Paragraph 0070-0077
(2020/02/27)
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- Direct Alkenylation of 2-Methylquinolines with Aldehydes through Synergistic Catalysis of 1,3-Dimethylbarbituric Acid and HOAc
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An efficient and practical direct alkenylation of 2-methylquinolines with aldehydes has been achieved through a novel synergistic organocatalysis. The HOAc- activated 2-methylquiolines undergo a Michael addition to 1,3-dimethylbarbituric acid-activated aldehydes, followed by a retro-Michael addition to release 1,3-dimethylbarbituric acid and the target products. The transformation produced various 2-alkenylquinolines with good to excellent yields and featured mild reaction conditions, atom- and step-economy, good functional group tolerance, and operational simplicity. (Figure presented.).
- Liang, En,Wang, Junqi,Wu, Yinrong,Huang, Liangbin,Yao, Xingang,Tang, Xiaodong
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supporting information
p. 3619 - 3623
(2019/07/10)
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- Nickel-Catalyzed Direct Alkenylation of Methyl Heteroarenes with Primary Alcohols
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An efficient nickel-catalyzed acceptorless dehydrogenative coupling of methyl-substituted heteroarenes with primary alcohols is achieved using an in situ generated complex of inexpensive NiBr2 and readily available 8-aminoquinoline picolinic amide ligand. The protocol is operationally simple and scalable and furnishes a series of high-value 2-alkenylheteroarenes in good yields (up to 88percent) with exclusive E-selectivity. The reaction proceeds with the release of water and molecular hydrogen, which was analyzed through gas chromatography to validate the reaction mechanism. ?
- Baidya, Mahiuddin,Ramakrishna, Isai,Ramalingam, Bose Muthu
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p. 9819 - 9825
(2019/08/26)
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- Synthesis of (E)-2-Alkenylazaarenes via Dehydrogenative Coupling of (Hetero)aryl-fused 2-Alkylcyclic Amines and Aldehydes with a Cobalt Nanocatalyst
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To date, the synthesis of (E)-2-alkenylazaarenes via the condensation of 2-methyl N-heteroarenes with aldehydes or their equivalents has been well demonstrated. However, the direct formation of such a class of useful compounds from extensively distributed 2-alkylcyclic amine motifs remains an unresolved goal. Herein, by employing the nitrogen-silica-doped carbon (Vulcan XC-72R) as the support, we have developed a low-loading cobalt nanocatalyst (Co/N-Si-C). The combination of such a catalyst with p-nitrobenzoic acid and molecular O2 exhibits excellent catalytic performance towards the dehydrogenative coupling of (hetero)aryl-fused 2-alkylcyclic amines with aldehydes to afford the (E)-2-alkenylazaarenes. In the reaction, effective capture of the partially dehydrogenated cyclic amine motifs appears to be the key strategy to address the issue of the chemoselectivity. The developed catalytic transformation proceeds with the merits of broad substrate scope, good functional group tolerance, high atom-efficiency, use of an earth-abundant and reusable cobalt catalyst and molecular O2 as a green oxidant, which offers an important basis for the direct conversion of inert cyclic amine units into the functional frameworks.
- Zhou, Changjian,Tan, Zhenda,Jiang, Huanfeng,Zhang, Min
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p. 2887 - 2892
(2018/05/03)
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- Manganese-Catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-Substituted N-Heteroarenes with Alcohols
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Catalysis with earth-abundant transition metals is an option to help save our rare noble-metal resources and is especially interesting when novel reactivity or selectivity patterns are observed. We report here on a novel reaction, namely the dehydrogenative alkylation or α-olefination of alkyl-substituted N-heteroarenes with alcohols. Manganese complexes developed in our laboratory catalyze the reaction with high efficiency whereas iron and cobalt complexes stabilized by the same ligands are essentially inactive. Hydrogen is liberated during the reaction, and bromine and iodine functional groups as well as olefins are tolerated. A variety of alkyl-substituted N-heteroarenes can be functionalized, and benzylic and aliphatic alcohols undergo the reaction.
- Zhang, Guoying,Irrgang, Torsten,Dietel, Thomas,Kallmeier, Fabian,Kempe, Rhett
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supporting information
p. 9131 - 9135
(2018/06/04)
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- A trans-substituted olefin preparation method (by machine translation)
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This invention relates to a trans-substituted olefin preparation method, which belongs to the technical field of organic chemical synthesis. The method adopts the simple alcohol and methyl nitrogen-containing heterocyclic as the starting material, by transition metal-catalyzed alkene base reaction, to obtain trans-substituted olefin compound. The reaction raw material, catalyst and additives is cheap, simple synthesis technology, greatly reduces the cost of synthesizing; mild reaction conditions, high yield, easy industrialization; the reaction of raw materials and catalyst cleaning toxic, small pollution to the environment. The trans-substituted olefin compound and its derivatives as an important fine chemicals, in the medical, agricultural chemicals, perfume and photoelectric and other industries have wide application. (by machine translation)
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Paragraph 0178; 0179; 0181; 0182
(2018/07/30)
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- Manganese-Catalyzed Direct Olefination of Methyl-Substituted Heteroarenes with Primary Alcohols
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Herein, we present the first catalytic direct olefination of methyl-substituted heteroarenes with primary alcohols through an acceptorless dehydrogenative coupling. The reaction is catalyzed by a complex of the earth-abundant transition metal manganese that is stabilized by a bench-stable NNN pincer ligand derived from 2-hydrazinylpyridine. The reaction is environmentally benign, producing only hydrogen and water as byproducts. A large number of E-disubstituted olefins were selectively obtained with high efficiency.
- Barman, Milan K.,Waiba, Satyadeep,Maji, Biplab
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supporting information
p. 9126 - 9130
(2018/07/25)
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- Use of nitrogen-containing heterocyclic radical substituted alkene compounds
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The invention relates to new use of a series of nitrogen-containing heterocyclic radical substituted alkene compounds, and more specifically relates to use of the compounds represented by general formula a or salts thereof in bioimaging, pH value detection, biomacromolecule detection or cell microenvironment detection, wherein Z, S1, S2 and R1 are defined as the specification. The compounds are utilized as the fluorescent dye for bioimaging, fluorescent pH probe for pH value detection and/or diagnostic agent for tumor cell detection. The compounds involved in the invention have excellent imaging effect, and shows the single component multicolor property, can be used for single component multicolor imaging or conventional imaging, etc., and haves enormous application prospect in bioimaging and tumor detection. (formula a).
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Paragraph 0216-0218; 0238-0239
(2017/09/12)
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- Iodine-Catalyzed Direct C-H Alkenylation of Azaheterocycle N-Oxides with Alkenes
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An efficient and regioselective alkenylation of azaheterocycle N-oxides with alkenes catalyzed by iodine under metal- and external oxidant-free reaction conditions has been developed. A variety of (E)-2-styrylazaheterocycles have been produced in moderate
- Zhang, Zhenhao,Pi, Chao,Tong, Heng,Cui, Xiuling,Wu, Yangjie
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supporting information
p. 440 - 443
(2017/02/10)
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- Direct alkenylation of alkylazaarenes with aldehydes through C(sp3)-H functionalization under catalytic InCl3 activation
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Under the influence of InCl3 as a Lewis acid catalyst, a methodology on the C(sp3)-H functionalization of alkylazaarenes has been demonstrated through the activation of benzylic C-H bonds towards their addition reaction with the appropriate electrophiles. This methodology was chiefly applied in the direct alkenylation of primary and secondary benzylic C-H bonds of alkylazaarenes with aldehydes. A variety of alkenyl products were afforded in generally good yields including the starting alkenyl intermediate used in the synthesis of montelukast and other related molecules.
- Jamal, Zaini,Teo, Yong-Chua,Lim, Gina Shiyun
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p. 2132 - 2138
(2016/04/19)
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- Facile synthesis of 2-alkenylazaarenes via dehydrative coupling of 2-methylazaarenes with aldehydes ‘on water’
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A catalyst-free dehydrative coupling of 2-methylazaarenes with aldehydes ‘on water’ has been developed for efficient synthesis of (E)-2-alkenylazaarenes. The challenging addition/dehydration of aliphatic aldehyde was successfully implemented using water as a solvent. A variety of 2-methylazaarenes, aromatic and aliphatic aldehydes were well tolerated.
- Fu, Shiheng,Wang, Liang,Dong, Haoxun,Yu, Junqiang,Xu, Lubin,Xiao, Jian
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supporting information
p. 4533 - 4536
(2016/09/23)
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- C(sp3)-H functionalization of methyl azaarenes: a calcium-catalyzed facile synthesis of (E)-2-styryl azaarenes and 2-aryl-1,3-bisazaarenes
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Alkaline earth (Ca2+) catalyzed sp3 C-H functionalization of methyl azaarenes for the synthesis of biologically important (E)-2-styryl azaarenes, 2-aryl-1,3-bisazaarenes and 3,3-bisazaarenyl indolinones has been described. Initially methyl azaarenes react with aryl aldehydes to give β-hydroxy derivatives, which undergo Ca(II) catalyzed thermodynamic elimination to give the styryl azaarenes in a single step. Similarly it may undergo SN1 reaction to give 2-aryl-1,3-bisazaarenes and 3,3-bisazaarenyl indolinones (if isatin used as the electrophile). This green synthetic methodology enjoys the simple reaction procedures, solvent free conditions, step economy, substrate diversity and high yields of the products in short time.
- Yaragorla, Srinivasarao,Singh, Garima,Dada, Ravikrishna
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supporting information
p. 5924 - 5929
(2015/11/02)
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- Regioselective Metal-Free Cross-Coupling of Quinoline N -Oxides with Boronic Acids
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A novel and operationally simple one-step C-H bond functionalization of quinoline N-oxides to 2-substituted quinolines was developed. This approach enables the regioselective functionalization under external oxidant- and metal-free conditions. The developed transformation represents the first application of the Petasis reaction in functionalization of heterocycles.
- Bering, Luis,Antonchick, Andrey P.
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p. 3134 - 3137
(2015/06/30)
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- Iron-catalyzed C(sp3)-H functionalization of methyl azaarenes: A green approach to azaarene-substituted α- Or β-hydroxy carboxylic derivatives and 2-alkenylazaarenes
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Bioactive azaarene-substituted lactic acids, β-hydroxy esters, 3-hydroxy-2H-indol-2-ones, and 2-alkenylazaarenes were prepared in moderate-to-excellent yields via C(sp3)-H functionalization of methyl azaarenes with carbonyl compounds in the presence of iron(ii) acetate as an inexpensive, nontoxic, efficient catalyst. The application of this atom-, step-economic, and environmentally friendly method was demonstrated by a gram-scale synthesis of 3-[(E)-2-(7-chloroquinolin-2-yl)vinyl]benzaldehyde, a key intermediate of leukotriene receptor antagonist (Montelukast).
- Pi, Danwei,Jiang, Kun,Zhou, Haifeng,Sui, Yuebo,Uozumi, Yasuhiro,Zou, Kun
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p. 57875 - 57884
(2015/01/08)
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- Cobalt-catalyzed direct alkenylation of 2-methylquinolines with aldehydes via C(sp3)-H functionalization in water
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The direct C(sp3)-H alkenylation of 2-methylquinolines with aldehydes as a simple methodology to afford 2-alkenylated quinolines is reported. In the presence of catalytic CoCl2 in water, the economically and ecologically sound transformation is proposed to proceed via the direct benzylic addition to the aldehyde followed by an elimination step to provide 2-alkenylated quinolines in good to excellent yield of up to 95%. Georg Thieme Verlag Stuttgart New York.
- Jamal, Zaini,Teo, Yong-Chua
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supporting information
p. 2049 - 2053
(2014/11/08)
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- Catalyst-free synthesis of (E)-2-alkenylquinoline derivatives via C(sp3)-H functionalization of 2-methylquinolines
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This Letter described a facile approach to synthesize (E)-2-alkenylquinoline derivatives via C(sp3)-H functionalization of 2-methylquinolines under catalyst-free conditions. A variety of electronically and sterically diverse 2-methyl quinoline and aromatic aldehydes were well tolerated.
- Xu, Lubin,Shao, Zhuzhou,Wang, Liang,Zhao, Huaili,Xiao, Jian
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supporting information
p. 6856 - 6860
(2015/01/09)
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- Synthesis and photophysical properties of novel fluorescent quinoline-based aryl substituted styryl systems
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Synthesis of (E)-2-(4-bromostyryl)quinoline has been easily achieved by an acid catalysed condensation of 2-methylquinoline with 4-bromobenzaldehyde. Various boronic acid derivatives reacted with (E)-2-(4-bromostyryl)quinoline to afford a series of novel
- Li, Qian,Li, Bao,Liu, Bin,Yu, Mingxin
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experimental part
p. 379 - 381
(2010/11/03)
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- Synthesis and photophysical properties of conjugated quinolines
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Aryl halides were prepared by condensation of 2-methylquinoline and bromo- or chloro-arylaldehydes in acetic anhydride. Diarylamines reacted with the aryl halides to afford novel triarylamine derivatives using Pd(OAch/P (o-tolylh as catalyst. These compou
- Vue, Voufeng,Vu, Mingxin,Zhu, Longguan
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experimental part
p. 427 - 429
(2009/12/25)
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