- Copper-catalyzed rapid C-H nitration of 8-aminoquinolines by using sodium nitrite as the nitro source under mild conditions
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A mild, rapid and efficient method for copper-catalyzed nitration of quinolines at the C5 or C7 position was reported firstly by using sodium nitrite as the nitro source. A series of nitrated quinoline derivatives were achieved in moderate to good yields
- Zhu, Xiaolei,Qiao, Li,Ye, Pingping,Ying, Beibei,Xu, Jun,Shen, Chao,Zhang, Pengfei
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Read Online
- Site-selective and metal-free C–H nitration of biologically relevant N-heterocycles
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The site-selective and metal-free C–H nitration reaction of quinoxalinones and pyrazinones as biologically important N-heterocycles with t-butyl nitrite is described. A wide range of quinoxalinones were efficiently applied in this transformation, providin
- Moon, Junghyea,Ji, Hyun Ku,Ko, Nayoung,Oh, Harin,Park, Min Seo,Kim, Suho,Ghosh, Prithwish,Mishra, Neeraj Kumar,Kim, In Su
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p. 1012 - 1023
(2021/10/20)
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- Light-Controlled Tyrosine Nitration of Proteins
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Tyrosine nitration of proteins is one of the most important oxidative post-translational modifications in vivo. A major obstacle for its biochemical and physiological studies is the lack of efficient and chemoselective protein tyrosine nitration reagents. Herein, we report a generalizable strategy for light-controlled protein tyrosine nitration by employing biocompatible dinitroimidazole reagents. Upon 390 nm irradiation, dinitroimidazoles efficiently convert tyrosine residues into 3-nitrotyrosine residues in peptides and proteins with fast kinetics and high chemoselectivity under neutral aqueous buffer conditions. The incorporation of 3-nitrotyrosine residues enhances the thermostability of lasso peptide natural products and endows murine tumor necrosis factor-α with strong immunogenicity to break self-tolerance. The light-controlled time resolution of this method allows the investigation of the impact of tyrosine nitration on the self-assembly behavior of α-synuclein.
- Long, Tengfang,Liu, Lei,Tao, Youqi,Zhang, Wanli,Quan, Jiale,Zheng, Jie,Hegemann, Julian D.,Uesugi, Motonari,Yao, Wenbing,Tian, Hong,Wang, Huan
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supporting information
p. 13414 - 13422
(2021/05/12)
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- Metal-free regioselective nitration of quinoxalin-2(1H)-ones withtert-butyl nitrite
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A metal-free coupling of quinoxalin-2(1H)-ones withtert-butyl nitrite has been developed. Distinctly from the previous functionalization of quinoxalin-2(1H)-ones, this nitration reaction took place selectively at the C7 or C5 position of the phenyl ring, affording a series of 7-nitro and 5-nitro quinoxalin-2(1H)-ones in moderate to good yields. Preliminary mechanistic studies revealed that the reaction may involve a radical process.
- Guo, Yu,Jiang, Hong,Li, Xue-Lin,Li, Yi-Na,Liu, Yunmei,Wang, Zhen,Wu, Jin-Bo,Zeng, Yao-Fu
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supporting information
p. 10554 - 10559
(2021/12/27)
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- AgNO3as Nitrogen Source for Cu-Catalyzed Cyclization of Oximes with Isocyanates: A Facile Route to N-2-Aryl-1,2,3-triazoles
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A versatile copper-catalyzed [3 + 1 + 1] annulation of oximes and isocyanates with AgNO3 is described. In this conversion, AgNO3 and isocyanates instead of conventional azide or diazonium reagents were used as the nitrogen source. This three-component transformation was achieved by cleaving N-O/C-H/C-N bonds and building CN/N-N bonds, which provides a strategy to prepare N-2-aryl-1,2,3-triazoles with a good substrate and functional compatibility.
- Liang, Jingwen,Rao, Yingqi,Zhu, Weidong,Wen, Tingting,Huang, Junjie,Chen, Zhichao,Chen, Lu,Li, Yibiao,Chen, Xiuwen,Zhu, Zhongzhi
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supporting information
p. 7028 - 7032
(2021/09/14)
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- Pd-Catalyzed Reductive Cyclization of Nitroarenes with CO2 as the CO Source
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A reductive amination process that constructs indoles, carbazoles or benzimidazoles from nitroarenes – irrespective of their electronic or steric nature – was developed that uses CO2 as the source of CO. The process is robust, tolerating common gaseous components of flue gas (H2S, SO2, NO and H2O) without adversely affecting the reductive cyclization.
- Guan, Xinyu,Zhu, Haoran,Zhao, Yingwei,Driver, Tom G.
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supporting information
p. 57 - 60
(2019/12/11)
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- Method for preparing nitroolefin from aryl ethane and nitrate
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According to the method, aryl ethane and nitrate, which are cheap and easy to obtain, are used as raw materials, and the E-nitroolefin compound is synthesized through a dehydrogenation nitration reaction of copper/silver catalyzed aryl ethane under the ox
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Paragraph 0063-0066
(2020/10/05)
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- Synthesis of N-Heterocycles by Reductive Cyclization of Nitroalkenes Using Molybdenum Hexacarbonyl as Carbon Monoxide Surrogate
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The development of a method that uses molybdenum hexacarbonyl [Mo(CO)6] as carbon monoxide (CO) surrogate for the palladium-catalyzed reductive cyclization of nitroalkenes into indoles or thienopyrroles is reported. Several types of nitroalkenes could be transformed into the desired products in excellent yields and in most cases with complete regioselectivities and higher yields than those previously reported with palladium/CO system.
- Su, Zhiyou,Liu, Bo,Liao, Hongze,Lin, Hou-Wen
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supporting information
p. 4059 - 4066
(2020/06/21)
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- Synthetic Diversity from a Versatile and Radical Nitrating Reagent
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We leverage the slow liberation of nitrogen dioxide from a newly discovered, inexpensive succinimide-derived reagent to allow for the C?H diversification of alkenes and alkynes. Beyond furnishing a library of aryl β-nitroalkenes, this reagent provides unparalleled access to β-nitrohydrins and β-nitroethers. Detailed mechanistic studies strongly suggest that a mesolytic N?N bond fragmentation liberates a nitryl radical. Using in situ photo-sensitized, electron paramagnetic resonance spectroscopy, we observed direct evidence of a nitryl radical in solution by nitrone spin-trapping. To further exhibit versatility of N-nitrosuccinimide under photoredox conditions, the late-stage diversification of an extensive number of C?H partners to prepare isoxazolines and isoxazoles is presented. This approach allows for the formation of an in situ nitrile oxide from a ketone partner, the presence of which is detected by the formation of the corresponding furoxan when conducted in the absence of a dipolarophile. This 1,3-dipolar cycloaddition with nitrile oxides and alkenes or alkynes proceeds in a single-operational step using a mild, regioselective, and general protocol with broad chemoselectivity.
- Zhang, Kun,Jelier, Benson,Passera, Alessandro,Jeschke, Gunnar,Katayev, Dmitry
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supporting information
p. 12929 - 12939
(2019/09/17)
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- NaNO2/K2S2O8-mediated Selective Radical Nitration/Nitrosation of Indoles: Efficient Approach to 3-Nitro- and 3-Nitrosoindoles
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JPZ acknowledges financial support from the National Natural Science Foundation of China (No. 21172163, 21472133), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), and Key Laboratory of Organic Synthesis of Jiangsu Province (KJS1749). (Figure presented.).
- Shoberu, Adedamola,Li, Cheng-Kun,Tao, Ze-Kun,Zhang, Guo-Yu,Zou, Jian-Ping
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supporting information
p. 2255 - 2261
(2019/04/13)
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- Difunctionalization of the C-N Bond through tert-Butylnitrite-Initiated C-N Cleavage of 1,2,3,4-Tetrahydroisoquinolines and N, N′-Diarylimidazolidines under Transition-Metal-Free Conditions
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Difunctionalization of the saturated C-N bond of 1,2,3,4-tetrahydroisoquinolines and N,N′-diarylimidazolidines was achieved using TBN as the metal-free initiator, providing a series N-nitrosoaminoaldehydes in high yields. Mechanistic study shows that the TBN-derived tBuO radical initiated the sp3 C-H bond activation, and the C-N bond cleavage was mediated by an iminium intermediate. This reaction provided a new way to cleave an inert C-N bond under mild and metal-free conditions, realizing the construction of molecular complexity through difunctionalization of the C-N bond.
- Sun, Zheng,Ji, Honghe,Shao, Yu,He, Kaixuan,Zhang, Yuxian,Yuan, Yu,Jia, Xiaodong
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p. 12292 - 12300
(2019/10/11)
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- Preparation method of nitroolefin derivative with nitrate as nitro source
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The invention relates to a nitroolefin derivative with nitrate as nitro source and a preparation method thereof. Under the atmosphere of nitrogen, an olefin compound, nitrate, trimethylchlorosilane (TMSC1) and copper salt are stirred in acetonitrile at 0-30 DEG C; in addition, the reaction degree is monitored by using a TLC point plate; after the olefin compound is completely consumed, alkali is added to an obtained mixture to be stirred for 20-30 min; then after a solvent is removed from an obtained mixture by using a rotary evaporator, the nitroolefin derivative can be obtained through silicagel column purification. Compared with the prior art, the nitroolefin derivative with the nitrate as the nitro source, provided by the invention, has the advantages of mild reaction condition, high yield, high E type selectivity and the like.
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Paragraph 0042; 0049-0054; 0106-0108
(2019/08/20)
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- Iron(III) nitrate-induced aerobic and catalytic oxidative cleavage of olefins
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Microwave-assisted catalytic oxidative cleavage of olefins using Fe(NO3)3·9H2O under O2 is reported. This reaction system is particularly effective when 9-benzylidene-9H-fluorene derivatives are used as substrates even though they are tri- and tetra-substituted olefins.
- Amaya, Toru,Fujimoto, Hayato
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supporting information
p. 2657 - 2660
(2018/06/04)
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- Autoinductive conversion of α,α-diiodonitroalkanes to amides and esters catalysed by iodine byproducts under O2
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Studies to convert nitroalkanes into amides and esters using I2 and O2 revealed in situ-generated iodine species facilitate the homolytic C-I bond cleavage of α,α-diiodonitroalkanes, arguably in an autoinductive or autocatalytic manner. Consequently, we devised a rapid and economical I2/O2-based method to synthesise sterically hindered esters directly from primary nitroalkanes.
- Li, Jing,Lear, Martin J.,Hayashi, Yujiro
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supporting information
p. 6360 - 6363
(2018/06/21)
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- Fe(III)/Pyridine-Mediated Decarboxylative Nitration of α,β-Unsaturated Acids with Iron Nitrate
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A novel and efficient method for the synthesis of (E)-nitroolefins in moderate to excellent yields is developed by Fe(III)/pyridine-mediated decarboxylative nitration of α,β-unsaturated acids with iron nitrate. A series of α,β-unsaturated acids are well tolerated in this procedure.
- Yang, Zan,Li, Jiao,Hua, Jie,Yang, Tao,Yi, Jianmin,Zhou, Congshan
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supporting information
p. 1079 - 1082
(2017/05/19)
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- In order to iodide is one pot synthesis nitryl source α, β - unsaturated nitro olefin derivatives (by machine translation)
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The present invention discloses a one-pot synthesis nitryl source iodide is α, β - unsaturated nitro olefin derivatives, vinyl compounds containing four aryl ferrous (III), iodide and tertiary-butyl hydrogen peroxide in acetonitrile solution system a pot of reaction, generating α, β - unsaturated nitro olefin derivatives; the method to achieve the under mild reaction conditions, high yield with high stereo selectivity of the E synthesis of α, β - unsaturated nitro olefin. (by machine translation)
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Paragraph 0122-0125; 0129-0131
(2017/09/01)
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- Α, β - unsaturated nitro olefin derivative synthesis method (by machine translation)
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The invention discloses a α, β - unsaturated nitro olefin derivative synthesis method, vinyl compounds containing four aryl ferrous (III), ammonium halide and tertiary-butyl hydrogen peroxide in the system of the one-pot reaction, generating α, β - unsaturated nitro olefin derivatives; the method to achieve the under mild reaction conditions, high yield with high stereo selectivity of the E synthesis of α, β - unsaturated nitro olefin. (by machine translation)
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Paragraph 0027; 0034; 0124; 0126; 0130; 0131; 0132
(2017/09/05)
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- K2S2O8-mediated nitration of alkenes with NaNO2 and 2,2,6,6-tetramethylpiperidine-1-oxyl: Stereoselective synthesis of (E)-nitroalkenes
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A transition-metal-free nitration of alkenes with NaNO2 in the presence of K2S2O8 and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) is developed. The transformation exhibits a broad substrate scope and good functional group tolerance, thus providing a new and expedient protocol for stereoselective synthesis of (E)-nitroalkenes with moderate to good yields. Moreover, the nitration processes of (E)- and (Z)-stilbene are also studied: even though the proportion of substrates is different, the E/Z ratio of the products is basically the same. Based upon experimental observations, a possible reaction mechanism is proposed.
- Zhao, An,Jiang, Qing,Jia, Jing,Xu, Bin,Liu, Yufeng,Zhang, Mingzhong,Liu, Qiang,Luo, Weiping,Guo, Cancheng
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supporting information
p. 80 - 84
(2015/12/23)
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- Traceless directing group mediated branched selective alkenylation of unbiased arenes
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Owing to the synthetic importance of branched olefinated products, we report palladium catalyzed formation of branched olefins facilitated by a C-H activation based protocol. This involves selective insertion of olefins and subsequent decarboxylation using a completely unbiased benzene ring as the starting precursor. The significance of the protocol has been further highlighted by exhibition of functionality tolerance along with a late-stage modification of the branched olefinated products leading to the formation of other functionalized molecules.
- Agasti, Soumitra,Dey, Aniruddha,Maiti, Debabrata
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supporting information
p. 12191 - 12194
(2016/10/21)
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- Copper Nitrate Mediated Regio- and Stereoselective Difunctionalization of Alkynes: A Direct Approach to α-Chloro-β-nitroolefins
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An efficient copper nitrate mediated chloronitration reaction was developed for the direct synthesis of α-chloro-β-nitroolefins with high regio- and stereoselectivity from simple alkynes and low toxic stannous chloride. This protocol provides a direct access to polysubstituted alkenes with operational simplicity, good functional group tolerance, and a wide substrate scope. Various applications of given products allowed the straightforward assembly of molecular complexity and indicated them as promising and valuable building blocks in organic synthesis.
- Gao, Mingchun,Xu, Bin
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supporting information
p. 4746 - 4749
(2016/09/28)
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- Effective nitration of anilides and acrylamides by tert-butyl nitrite
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Nitro compounds are important intermediates in synthetic organic chemistry and the chemical industry. Herein, the efficient copper-catalyzed [10% Cu(NO3)2·3H2O] nitration of anilides was developed by using TBN (tert-butyl nitrite) as a nitrating reagent to give the corresponding nitro-substituted aromatic products in good to excellent yields. The use of TBN also led to the selective nitration of acrylamides at room temperature to afford only the (E) isomer of the nitration product. A series of anilides and acrylamides with a broad array of functional groups were well-tolerated by this procedure. This synthetic method has many advantages, which include inexpensive starting materials, mild reaction conditions, a fast reaction rate, and high yields. A mechanistic investigation indicates that a nitro radical, which is generated from the thermal homolysis of TBN, is involved in the two nitration processes. The efficient nitration of both anilides and acrylamides was achieved by using TBN (tert-butyl nitrite) as a metal-free nitrating reagent. This synthetic method has many advantages such as mild reaction conditions, a fast reaction rate, good to excellent yields, and a broad substrate scope. Our investigation indicates that a nitro radical is involved in the reaction mechanism.
- Ji, Yi-Fei,Yan, Hong,Jiang, Qi-Bai
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p. 2051 - 2060
(2015/03/18)
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- Metal-free regioselective C-3 nitration of quinoline N-oxides with tert-butyl nitrite
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A direct and eco-friendly nitration methodology to synthesize 3-nitroquinoline N-oxides from quinoline N-oxides using tert-butyl nitrite as both the nitro source and oxidant has been developed. Although this reaction undergoes a free radical process, it exhibits high regioselectivity and can be smoothly scaled up to gram scale. This journal is
- Zhao, Jingjing,Li, Pan,Xia, Chungu,Li, Fuwei
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p. 32835 - 32838
(2015/04/27)
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- Synthesis of Indoles by Palladium-Catalyzed Reductive Cyclization of β-Nitrostyrenes with Carbon Monoxide as the Reductant
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An efficient catalytic cyclization of β-nitrostyrenes to indoles was developed. The reaction was applied to the synthesis of 3-arylindoles and 2-alkylindoles. Given that in the latter case the starting β-nitrostyrenes can be easily obtained by a Henry reaction, the present method allows indoles to be obtained in a two-step sequence starting from cheap reactants.
- Ferretti, Francesco,El-Atawy, Mohamed A.,Muto, Stefania,Hagar, Mohamed,Gallo, Emma,Ragaini, Fabio
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supporting information
p. 5712 - 5715
(2015/09/15)
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- Cu-catalyzed selective cascade sp3 C-H bond oxidative functionalization towards isoxazoline derivatives
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The first Cu-catalyzed cascade sp3 C-H bond oxidative functionalization of the 2-ethylazaarenes has been developed. The two different sp3 C-H bonds in 2-ethylazaarenes are selectively oxidized and four new types of bonds (CO, CN, C-C, C-O) are constructed in one operation. Starting from the simple substrates and cheap nitro source, this reaction provides an efficient approach to produce new kinds of isoxazolines.
- Wang, Gang-Wei,Cheng, Ming-Xing,Ma, Ran-Song,Yang, Shang-Dong
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supporting information
p. 6308 - 6311
(2015/04/14)
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- Efficient and stereoselective nitration of mono- and disubstituted olefins with AgNO2 and TEMPO
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Nitroolefin is a common and versatile reagent. Its synthesis from olefin is generally limited by the formation of mixture of cis and trans compounds. Here we report that silver nitrite (AgNO2) along with TEMPO can promote the regio- and stereoselective nitration of a broad range of olefins. This work discloses a new and efficient approach wherein starting from olefin, nitroalkane radical formation and subsequent transformations lead to the desired nitroolefin in a stereoselective manner.
- Maity, Soham,Manna, Srimanta,Rana, Sujoy,Naveen, Togati,Mallick, Arijit,Maiti, Debabrata
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supporting information
p. 3355 - 3358
(2013/04/10)
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- Synthesis of substituted nitroolefins: A copper catalyzed nitrodecarboxylation of unsaturated carboxylic acids
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A novel, mild and convenient method for the nitrodecarboxylation of substituted cinnamic acid derivatives to their nitroolefins is achieved using a catalytic amount of CuCl (10 mol%) and tert-butyl nitrite (2 equiv.) as a nitrating agent in the presence of air. This reaction provides a useful method for the synthesis of β,β-disubstituted nitroolefin derivatives, which are generally difficult to access from other conventional methods. Additionally, this reaction is selective as the E-isomer of the acid derivatives furnishes the corresponding E-nitroolefins. One more salient feature of the method is, unlike other methods, no metal nitrates or HNO3 are employed for the transformation.
- Rokade, Balaji V.,Prabhu, Kandikere Ramaiah
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p. 6713 - 6716
(2013/10/01)
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- Polymer nitrile N-oxides directed toward catalyst- and solvent-free click grafting
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A general method for the one-pot synthesis of stable polymer nitrile N-oxides was developed by a combination of 1,1-diphenylnitroethene with a living anionic polymer. The polymer nitrile N-oxide served as a facile and effective grafting tool for use with polymers containing unsaturated bonds in a catalyst-free and solvent-free [2+3] cycloaddition.
- Wang, Chen-Gang,Koyama, Yasuhito,Yonekawa, Morio,Uchida, Satoshi,Takata, Toshikazu
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supporting information
p. 7723 - 7725
(2013/09/02)
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- Versatile synthesis of α-substituted taurines from nitroolefins
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A series of 1-substituted and 1,1-disubstituted taurines were synthesized from nitroolefins via the Michael addition with sodium ethylxanthate, oxidation with performic acid, and reduction with hydrogen in the presence of palladium on carbon powder. The current route is a versatile and salt-free method for synthesis of both aliphatic and aromatic 1-substituted and 1,1-disubstituted taurines. Springer-Verlag 2010.
- Xu, Chuanxiang,Xu, Jiaxi
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scheme or table
p. 195 - 203
(2012/04/10)
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- Indole synthesis: palladium-catalyzed C-H bond amination via reduction of nitroalkenes with carbon monoxide
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Nitroalkenes have been called 'chemical chameleons' due to their versatility in numerous synthetic transformations. Herein, we describe the first transition metal-catalyzed transformation of conjugated nitroalkenes into indoles. Under mild reaction condit
- Hsieh, Tom H.H.,Dong, Vy M.
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experimental part
p. 3062 - 3068
(2009/09/05)
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- A selective and practical synthesis of nitroolefins
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A straightforward and general synthesis of nitroolefins from nitric oxide (NO) and olefins is presented. The direct nitration of aromatic olefins, allyl compounds, and acrylic acid derivatives proceeds smoothly at room temperature with high regioselectivity and good yields. The advantages of this novel procedure compared to established nitration procedures are demonstrated.
- Jovel, Irina,Prateeptongkum, Saisuree,Jackstell, Ralf,Vogl, Nadine,Weckbecker, Christoph,Beller, Matthias
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experimental part
p. 2493 - 2497
(2009/08/14)
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- Dithioacetal as a 1,1-zwitterion synthon. Synthesis of functionalized alkenes by the coupling of benzylic dithioacetals with another 1,1-zwitterion synthon
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Reaction of a dithioacetal sequentially with BuLi and alkyl bromide having an electron withdrawing substituent at the α-position followed by treatment with neutral alumina gives the corresponding olefination product in moderate to good yields.
- Tu, Hai-Yang,Liu, Yi-Hung,Wang, Yu,Luh, Tien-Yau
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p. 771 - 773
(2007/10/03)
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- Substituted 5-dinitromethyl-3-phenyl-1,2,4-oxadiazoles in reactions with arylethenes
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Reactions of substituted 5-dinitromethyl-3-phenyl-1,2,4-oxadiazoles with arylethenes of various nucleophilicity, number and position of substituents attached to the double bond give rise to nitroalkenes and secondary products resulting from α-nitroketones or nitroalcohols O-alkylation. The direction of transformations in the arising ion pair is governed predominantly by steric effects.
- Tyrkov
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p. 890 - 892
(2007/10/03)
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- Addition, Substitution, and Deoxygenation Reactions of α-Phenyl-β-nitrostyrenes with the Anions of Thiols and Diethyl Phosphite: Formation of Indoles by Reaction with Ethyl Phosphites
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Reaction of excess RS- (R=Ph, t-Bu) with Ph2C=C(SPh)NO2 in Me2SO form Ph2C=CHSR via conversion of the initial Michael-type adducts into Ph2C(SR)CH=NO2- and Ph2C=CHNO2.In a similar fashion, reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 forms initially mainly PhSP(O)(OEt)2 and Ph2CCH=NO2-, which upon acidic workup will yield the nitroalkane or the Nef reaction product, Ph2CCHO.The reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 also produces Ph2CCN via a Perkow-type reaction of the Michael adduct to yield Ph2CCH=N(O)OP(O)(OEt)2 as an intermediate.The nitrile is also formed from Ph2CCH(NO2)2 with (EtO)2PO- in (EtO)2P(O)H or Me2SO at 30 deg C and in >95percent yield by the reaction of (EtO)3P with Ph2CCH(NO2)2 at 150 deg C.Reaction of Ph2C=CHNO2 or Ph2CCH2NO2 with excess (EtO)PO- in Me2SO or (EtO)2P(O)H forms 3-(diethoxyphosphinyl)-2,2-diphenylaziridine by a process postulated to involve Ph2C=CHN(O-)OP(O)(OEt)2, Ph2C=CHNOP(O)(OEt)2-, and 2,2-diphenyl-2H-azirine.Similarly, Ph2C=C(SBu-t)NO2 and (EtO)2PO- give 3-(tert-butylthio)-2,2-diphenyl-2H-azirine in Me2SO or 2-(tert-butylthio)-3-phenylindole in (EtO)2P(O)H solution.Deoxygenation of Ph2C=C(X)NO2 to form the 2-X-3-phenylindoles occurs in high yield at 150 deg C in (EtO)3P with X=H, PhS, or t-BuS while 2-nitrro-3-phenylindole is formed from Ph2C=C(NO2)2 in (EtO)2P(O)H at 150 deg C.
- Russell, Glen A.,Yao, Ching-Fa,Tashtoush, Hasan I.,Russell, June E.,Dedolph, Douglas F.
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p. 663 - 669
(2007/10/02)
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- II. Thermal nitration of olefins with tetranitromethane. Evidence for homolytic initiation of a chain mechanism
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Tetranitromethane (TNM) reacts spontaneously with N-vinylcarbazole to afford the product of 1,2-addition.Under the same conditions, 9-vinylanthracene and other olefins do not react with TNM until they are deliberately stimulated by a short pulse of visible light.Photo-activation under these conditions is associated with the charge-transfer excitation of the olefin-TNM complex to produce NO2.The subsequent homolytic addition of NO2 to the olefinic donor, followed by electron transfer of the radical adduct, is responsible for the novel chain mechanism for TNM addition in Scheme 1.Homolytic initiation can also be achieved chemically with various additives such as the electron-rich ferrocene, N,N,N',N'-tetramethyl-1,4-phenylenediamine, and 5H-dibenzazepine which generate NO2 by dissociative electron attachment to TNM.The limited quanta of light and traces of chemical initiators indicate that the chain mechanism for the addition of TNM occurs with relatively long kinetic chain lengths.The mechanistic implications of the chain mechanism for the formation of various types of products is discussed in the context of olefin structures.
- Masnovi, J. M.,Kochi, J. K.
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p. 286 - 295
(2007/10/02)
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- FORMATION OF NITRO COMPOUNDS DURING THE NITROSATION OF OLEFINS BY ALKYL NITRITES
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Vicinal nitro alcohols and/or dinitro derivatives are formed in the reaction of olefins containing a quaternary carbon atom with alkyl nitrites in acetic acid.
- Yandovskii, V. N.,Ryabinkin, I. I.,Tselinskii, I. V.
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p. 1773 - 1775
(2007/10/02)
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- Reduction of 2,2-Diaryl-1-nitroethylenes : New Synthesis of 2,2-Diarylacetaldehydes and 1,1,4,4-Tetraarylbuta-1,3-dienes
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2,2-Diarylacetaldehydes (VII) have been obtained by selective and controlled reduction of 2,2-diaryl-1-nitroethylenes (IV) in acid medium, and also by acid hydrolysis of 2,2-diarylvinyl-N-acetamides (VI).Nitroalkenes (IV) have been prepared by the reaction of 2,2-diarylethylenes (I) with nitrous acid whereas N-acetamide derivatives (VI) have been obtained by reductive acetylation of the nitro compounds (IV).A number of 1,1,4,4-tetraarylbuta-1,3-dienes (XI) have been obtained by the condensation of 2,2-diarylacetaldehydes (VII) with appropriate 2,2-diarylethylenes (I).Structures of the products have been assigned on the basis of analytical data and chemical and spectral evidences.
- Tadros, Wadie,Awad, Sami B.,Sakla, Alfy B.,Abdul-Malik, Nadia F.,Armanious, Emili R.
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p. 199 - 202
(2007/10/02)
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