- Soluble guanylate cyclase stimulator, trans-4-methoxy-β-nitrostyrene, has a beneficial effect in monocrotaline-induced pulmonary arterial hypertension in rats
-
The soluble guanylate cyclase (sGC)/GMPc pathway plays an important role in controlling pulmonary arterial hypertension (PAH). We investigated whether the novel sGC stimulator trans-4-methoxy-β-nitrostyrene (T4MN), ameliorates monocrotaline (MCT)-induced
- Gonzaga-Costa, Karoline,Vasconcelos-Silva, Alfredo Augusto,Rodrigues-Silva, Matyelle Jussára,Rebou?a, Concei??o da Silva Martins,Duarte, Glória Pinto,Borges, Rosivaldo Santos,Magalh?es, Pedro Jorge Caldas,Lahlou, Saad
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- Metal-Free Deoxygenation of Chiral Nitroalkanes: An Easy Entry to α-Substituted Enantiomerically Enriched Nitriles
-
A metal-free, mild and chemodivergent transformation involving nitroalkanes has been developed. Under optimized reaction conditions, in the presence of trichlorosilane and a tertiary amine, aliphatic nitroalkanes were selectively converted into amines or nitriles. Furthermore, when chiral β-substituted nitro compounds were reacted, the stereochemical integrity of the stereocenter was maintained and α-functionalized nitriles were obtained with no loss of enantiomeric excess. The methodology was successfully applied to the synthesis of chiral β-cyano esters, α-aryl alkylnitriles, and TBS-protected cyanohydrins, including direct precursors of four active pharmaceutical ingredients (ibuprofen, tembamide, aegeline and denopamine).
- Pirola, Margherita,Faverio, Chiara,Orlandi, Manuel,Benaglia, Maurizio
-
supporting information
p. 10247 - 10250
(2021/06/18)
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- Catalytic Asymmetric Construction of Tertiary Carbon Centers Featuring an α-Difluoromethyl Group with CF2H-CH2-NH2as the "building Block"
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We report here for the first time a novel difluoromethylated ketimine building block condensed by thioisatin and difluoroethylamine, offering efficient access to a broad range of enantioenriched products bearing difluoroethylamine units (27 examples, ≤98% yield, >99% ee) in the presence of quinine-derived squaramide. Further transformation of the intermediate would generate a variety of versatile functional blocks like α-difluoromethyl amines, β-amino acid, and β-diamine with retention of the enantiomeric excess at the difluoromethyl-bound carbon.
- Gao, Fengyun,Guo, Yifei,Sun, Mengmeng,Wang, Yalan,Yang, Changyan,Wang, Yuqiang,Wang, Kairong,Yan, Wenjin
-
supporting information
p. 2584 - 2589
(2021/04/13)
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- Dipolar HCP materials as alternatives to DMF solvent for azide-based synthesis
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Hypercrosslinked polymers HCP-DMF and HCP-DMF-SO3H containing abundant and flexible DMF moieties were designed and synthesized. Benefitting from the solvation microenvironment provided by the pseudo-DMF moities, the polar HCPs manifested outstanding performances in the conversions of NaN3 to benzylic azides and 1,2,3-triazoles in EtOH (95%), respectively, avoiding the use of risky DMF and improving the separation processes of the products.
- Bai, Rongxian,Gao, Feng,Gu, Yanlong,Li, Minghao
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supporting information
p. 7499 - 7505
(2021/10/12)
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- Preparation method of beta-trans-nitroolefin
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The invention relates to a preparation method of beta-trans-nitroolefin. The method comprises: sequentially adding an olefin compound, a nitration reagent and a solvent into a reaction container, mixing the substances uniformly, and carrying out constant temperature reaction for 18h under an illumination condition to obtain a reaction solution; and sequentially carrying out drying, concentration and column chromatography treatment on the reaction solution to obtain the beta-trans-nitroolefin compound. The method is simple and practicable, low in cost and high in product yield, can realize large-scale production, and has good industrial application prospects in the aspects of functional organic material, bioactive compound and drug synthesis.
- -
-
Paragraph 0042-0045
(2020/06/17)
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- Ionic-Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles
-
Unprecedented in literature, the conversion of aryl alkenes into β-nitrostyrenes (2) or benzonitriles (3) with sodium nitrite can be governed by an appropriate choice of ionic liquid (IL) medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium-based ILs, such as [Bmim]Cl, that favor the C–H nitration leading to β-nitrostyrenes, while tetraalkylammonium-based ILs, such as TBAA, privilege the C=C bond cleavage affording benzonitriles. Besides a substrate scope, mechanistic hypotheses were provided on the origin of the different selectivity in the two kinds of ILs, based on their own tunable properties such as polarity, viscosity, and solvent cage effects.
- Casiello, Michele,Caputo, Daniela,Fusco, Caterina,Cotugno, Pietro,Rizzi, Vito,Dell'Anna, Maria Michela,D'Accolti, Lucia,Nacci, Angelo
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supporting information
p. 6012 - 6018
(2020/08/24)
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- Molecular Engineering of β-Substituted Oxoporphyrinogens for Hydrogen-Bond Donor Catalysis
-
A new class of bifunctional hydrogen-bond donor organocatalyst using oxoporphyrinogens having increased intramolecular hydrogen-bond donor distances is reported. Oxoporphyrinogens are highly non-planar rigid macrocycles containing a multiple hydrogen bond-forming binding site. In this work, we describe the first example of non-planar OxPs as hydrogen-bond donor catalysts prepared using a molecular engineering approach of the binding site for dual activation of substrates. The introduction of β-substituents is key to the catalytic activity and the catalysts are able to catalyze 1,4-conjugate additions and sulfa-Michael additions, as well as, Henry and aza-Henry reactions at low catalyst loadings (≤ 1 mol-%) under mild conditions. Preliminary mechanistic studies have been carried out and a possible reaction mechanism has been proposed based on the bi-functional activation of both substrates through hydrogen-bonding interactions.
- Chahal, Mandeep K.,Payne, Daniel T.,Matsushita, Yoshitaka,Labuta, Jan,Ariga, Katsuhiko,Hill, Jonathan P.
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supporting information
p. 82 - 90
(2020/01/02)
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- Biological evaluation and SAR analysis of novel covalent inhibitors against fructose-1,6-bisphosphatase
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Fructose-1,6-bisphosphatase (FBPase) is an attractive target for affecting the GNG pathway. In our previous study, the C128 site of FBPase has been identified as a new allosteric site, where several nitrovinyl compounds can bind to inhibit FBPase activity. Herein, a series of nitrostyrene derivatives were further synthesized, and their inhibitory activities against FBPase were investigated in vitro. Most of the prepared nitrostyrene compounds exhibit potent FBPase inhibition (IC50 3, CF3, OH, COOH, or 2-nitrovinyl were installed at the R2 (meta-) position of the benzene ring, the FBPase inhibitory activities of the resulting compounds increased 4.5–55 folds compared to those compounds with the same groups at the R1 (para-) position. In addition, the preferred substituents at the R3 position were Cl or Br, thus compound HS36 exhibited the most potent inhibitory activity (IC50 = 0.15 μM). The molecular docking and site-directed mutation suggest that C128 and N125 are essential for the binding of HS36 and FBPase, which is consistent with the C128-N125-S123 allosteric inhibition mechanism. The reaction enthalpy calculations show that the order of the reactions of compounds with thiol groups at the R3 position is Cl > H > CH3. CoMSIA analysis is consistent with our proposed binding mode. The effect of compounds HS12 and HS36 on glucose production in primary mouse hepatocytes were further evaluated, showing that the inhibition was 71% and 41% at 100 μM, respectively.
- Chen, Haifeng,Guo, Yanrong,Han, Xinya,Hu, Wei,Huang, Yunyuan,Ren, Yanliang,Tang, Zilong,Wang, Qi,Wei, Lin,Xia, Qinfei,Yan, Jufen
-
supporting information
(2020/07/23)
-
- Asymmetric synthesis of tetrahydropyran[3,2-c]quinolinones via an organocatalyzed formal [3 + 3] annulation of quinolinones and MBH 2-naphthoates of nitroolefin
-
An efficient asymmetric and enantio-swithchable organocatalytic [3 + 3] annulation reaction using MBH-2-naphthoates of nitroalkenes and 4-hydroxyquinolin-2(1H)-ones has been developed. Densely substituted tetrahydropyrano[3,2-c]quinolinones scaffolds with two adjacent stereogenic centers are obtained with high yield (up to 95% yield) and good stereoselectivities (up to >20:1 dr and 96% ee) in an enantio-switchable manner. Furthermore, gram scale synthesis was achieved and the nitro group could easily transform into an amino group without any appreciable loss in the diastereo- and enantioselectivity.
- Li, Jian,Hu, Qi-Long,Chen, Xue-Ping,Hou, Ke-Qiang,Chan, Albert S.C.,Xiong, Xiao-Feng
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supporting information
p. 697 - 700
(2019/09/30)
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- A photocatalyst-free photo-induced denitroalkylation of β-nitrostyrenes with 4-alkyl substituted Hantzsch esters at room temperature
-
A photocatalyst-free stereoselectively photo-induced strategy for the denitroalkylation of β-nitrostyrenes using 4-alkyl substituted Hantzsch esters as the alkyl source under xenon lamp irradiation is developed. The reaction proceeds at room temperature and affords the corresponding products in moderate to excellent yields. The oxidant di-t-butyl peroxide serves as an efficient radical initiator under irradiation of a Xenon lamp, initiating alkyl radicals from the 4-alkyl substituted Hantzsch esters.
- Duan, Chunying,Hao, Xinyu,Jin, Kun,Li, Yaming,Wang, Jiaao,Zhang, Rong,Zhang, Siyu
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supporting information
(2020/02/18)
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- NCC Pincer Ni (II) Complexes Catalyzed Hydrophosphination of Nitroalkenes with Diphenylphosphine
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An efficient NCC pincer Ni (II)-catalyzed hydrophosphination of nitroalkenes with diphenylphosphine has been developed. Under the optimized conditions, both (hetero)aromatic and aliphatic nitroalkenes were well tolerated, irrespective of electronic effect, to provide the corresponding products in up to 99% yield.
- Yan, Jing,Wang, Yan-Bing,Hou, Senyao,Shi, Linlin,Zhu, Xinju,Hao, Xin-Qi,Song, Mao-Ping
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- tert-Butyl Nitrite Mediated Nitro-Nitratosation of Internal Alkenes
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In an oxygen atmosphere tert-butyl nitrite (TBN) reacts with unsymmetrical internal benzylic alkenes giving nitro-nitratosation product exclusively. The γ-diaryl-substituted styrenes provided better yields compared to γ-alkyl-aryl-substituted styrenes. The higher yields for the former type of substrates is possibly dictated by the additional stability of benzylic radical due to the anchimeric assistance imparted by the γ-substituted phenyl ring. During oxidative nitration, the nitro (NO2) group adds at the non-benzylic site, whereas the nitrato group (ONO2) is attached at the relatively stable benzylic position. Under similar reaction conditions, α,β-unsaturated carboxylic acids, afforded nitroalkenes as the sole product.
- Mir, Bilal Ahmad,Rajamanickam, Suresh,Begum, Pakiza,Patel, Bhisma K.
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p. 2617 - 2625
(2020/05/08)
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- Metal-free, room temperature, acid-K2S2O8 mediated method for the nitration of olefins: An easy approach for the synthesis of nitroolefins
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Here, we have developed a simple, room temperature method for the nitration of olefins by using inexpensive sodium nitrite as a source of nitro groups in the presence of trifluoroacetic acid (TFA) and potassium persulfate (K2S2O8) under an open atmosphere. Styrenes and mono-substituted olefins give stereo-selective corresponding E-nitroolefins under optimized conditions, however, 1,1-bisubstituted olefins give a mixture of E- and Z-nitroolefins. The optimized conditions work well with electron-donating, electron-withdrawing, un-substituted and heterocyclic styrenes and mono-substituted olefins and give corresponding nitroolefins with good to excellent yields.
- Ambala, Srinivas,Singh, Rohit,Singh, Maninder,Cham, Pankaj Singh,Gupta, Ria,Munagala, Gurunadham,Yempalla, Kushalava Reddy,Vishwakarma, Ram A.,Singh, Parvinder Pal
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p. 30428 - 30431
(2019/10/04)
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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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- A chiral bicyclic skeleton-tethered bipyridine-Zn(OTf)2 complex as a Lewis acid: Enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes
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A conformationally rigid chiral bicyclic skeleton tethered bipyridine-Zn(OTf)2 complex facilitated the enantioselective Friedel-Crafts alkylation of indoles with trans-β-nitroarylalkenes in an enantioselective manner at elevated temperature. Indoles reacted smoothly with β-nitroarylalkenes to generate the corresponding 3-(2-nitroalkyl)indoles in good to excellent yields (up to 94%) with moderate to excellent enantioselectivities (up to 91%). The stereochemical outcome of the product from indole and trans-β-nitrostyrene in the presence of the CRCB tethered bipyridine-Zn(OTf)2 complex and the DFT calculation of the CRCB tethered bipyridine-Zn:trans-β-nitrostyrene complex support the si-face attack of indole on trans-β-nitrostyrene.
- Venkatanna, Kesa,Yeswanth Kumar, Santhakumar,Karthick, Muthupandi,Padmanaban, Ramanathan,Ramaraj Ramanathan, Chinnasamy
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p. 4077 - 4086
(2019/04/30)
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- Iodine monobromide catalysed regioselective synthesis of 3-arylquinolines from α-aminoacetophenones and: Trans -β-nitrostyrenes
-
A simple and efficient method for regioselective synthesis of 3-arylquinolines is described from α-aminoacetophenones and trans-β-nitrostyrenes using 20 mol% iodine monobromide as a catalyst in acetonitrile solvent at 80 °C. The present method involves tandem reaction of α-aminoacetophenones and trans-β-nitrostyrenes, formation of two new C-C bonds and cleavage of one C-C bond in a single step. The salient features of the protocol are metal- and oxidant-free reaction conditions, broad substrate scope, and good yields.
- Gattu, Radhakrishna,Mondal, Santa,Ali, Saghir,Khan, Abu T.
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supporting information
p. 347 - 353
(2019/01/10)
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- Mechanisms underlying the vasorelaxant effect of trans-4-methoxy-β-nitrostyrene in the rat mesenteric resistance arteries
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Mechanisms underlying the vasorelaxant effects of the synthetic nitro compound, trans-4-methoxy-β-nitrostyrene (T4MN) were studied in isolated small resistance arteries from spontaneously hypertensive rats (SHRs). T4MN caused vasorelaxation in endothelium
- Alves-Santos, Thayane Rebeca,Xavier, Fabiano Elias,Duarte, Gloria Pinto,dos Santos Borges, Rosivaldo,Magalh?es, Pedro Jorge Caldas,Lahlou, Saad
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p. 201 - 209
(2019/04/01)
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- Concerted catalysis by nanocellulose and proline in organocatalytic Michael additions
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Cellulose nanofibers (CNFs) have recently attracted much attention as catalysts in various reactions. Organocatalysts have emerged as sustainable alternatives to metal-based catalysts in green organic synthesis, with concerted systems containing CNFs that are expected to provide next-generation catalysis. Herein, for the first time, we report that a representative organocatalyst comprising an unexpected combination of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-oxidized CNFs and proline shows significantly enhanced catalytic activity in an asymmetric Michael addition.
- Ranaivoarimanana, Naliharifetra Jessica,Kanomata, Kyohei,Kitaoka, Takuya
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supporting information
(2019/04/05)
-
- Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex-Catalyzed Hydroarsination Reaction
-
Synthetic challenges have significantly slowed the development of the catalytic asymmetric hydroarsination reaction despite it being a highly attractive C?As bond formation methodology. In addition, there is a poor understanding of the main reaction steps in such reactions which limit further development in the field. Herein, key intermediates of the hydroarsination reaction catalyzed by a PCP NiII-Cl pincer complex are presented upon investigating the reaction with DFT calculations, conductivity measurements, NMR spectroscopy, and catalytic screening. The novel Ni–Cl–As interaction proposed was then contrasted against known NiII-catalyzed hydrophosphination reactions to highlight dissimilarities between them even though P and As share a close group relationship. Lastly, the asymmetric hydroarsination of nitroolefins was further developed to furnish a library of chiral organoarsines in up to 99 % yield and 80 % ee under mild conditions (?20 °C to RT) between 5 to 210 mins.
- Tay, Wee Shan,Lu, Yunpeng,Yang, Xiang-Yuan,Li, Yongxin,Pullarkat, Sumod A.,Leung, Pak-Hing
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supporting information
p. 11308 - 11317
(2019/08/07)
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- Poly(ethylene glycol) supported metal nitrates as well-organized reagents for hunsdiecker conversion of α,β-unsaturated acids to β-nitrostyrenes under solvent and acid-free conditions
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Poly(ethylene glycol) (PEG) supported metal nitrates such as ferric nitrate and manganese nitrate were accomplished as well-organized reagents for Hunsdiecker conversion of α,β-unsaturated acids to β-nitrostyrenes under acid-free and solvent free conditions using grindstone technique. However, in the case of unsaturated aliphatic acids, nitro alkene derivatives were obtained as products. PEG-400 was found the best among the other PEGs (PEG-200,300, 400, 600, 3000 and 6000) used in this protocol.
- Ramesh,Shylaja,Ramgopal,Rao, A. Sambashiva,Rajanna
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p. 1798 - 1800
(2019/07/17)
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- A Deprotonation Approach to the Unprecedented Amino-Trimethylenemethane Chemistry: Regio-, Diastereo-, and Enantioselective Synthesis of Complex Amino Cycles
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The first realization of the amino-trimethylenemethane chemistry is reported using a deprotonation strategy to simplify the synthesis of the amino-trimethylenemethane donor in two steps from commercial and inexpensive materials. A broad scope of cycloaddition acceptors (seven different classes) participated in the chemistry, chemo-, regio-, diastereo-, and enantioselectively generating various types of highly valuable complex amino cycles. Multiple derivatization reactions that further elaborated the initial amino cycles were performed without isolation of the crude product. Ultimately, we applied the amino-trimethylenemethane chemistry to synthesize a potential pharmaceutical in 8 linear steps and 7.5 % overall yield, which previously was achieved in 18 linear steps and 0.6 % overall yield.
- Trost, Barry M.,Wang, Youliang
-
supporting information
p. 11025 - 11029
(2018/07/30)
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- Base-catalyzed reactions enhanced by solid acids: Amine-catalyzed nitroaldol (Henry) reactions enhanced by silica gel or mesoporous silica SBA-15
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The reactions of various aldehydes with CH3NO2 catalyzed by Et3N, n-C6H13NH2, and Me2N(CH2)2NH2 were accelerated by the addition of silica gel to give aromatic (aliphatic) β-nitroalcohols, aromatic nitroalkenes, and aromatic 1,3-dinitroalkanes, respectively. Mesoporous silica SBA-15 showed higher activity than silica gel for the synthesis of aromatic nitroalkenes by the reactions of the corresponding aldehydes with CH3NO2 catalyzed by n-C6H13NH2.
- Tanemura, Kiyoshi,Suzuki, Tsuneo
-
supporting information
p. 392 - 396
(2017/12/28)
-
- Discovery of Cytochrome P450 4F11 Activated Inhibitors of Stearoyl Coenzyme A Desaturase
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Stearoyl-CoA desaturase (SCD) catalyzes the first step in the conversion of saturated fatty acids to unsaturated fatty acids. Unsaturated fatty acids are required for membrane integrity and for cell proliferation. For these reasons, inhibitors of SCD represent potential treatments for cancer. However, systemically active SCD inhibitors result in skin toxicity, which presents an obstacle to their development. We recently described a series of oxalic acid diamides that are converted into active SCD inhibitors within a subset of cancers by CYP4F11-mediated metabolism. Herein, we describe the optimization of the oxalic acid diamides and related N-acyl ureas and an analysis of the structure-activity relationships related to metabolic activation and SCD inhibition.
- Winterton, Sarah E.,Capota, Emanuela,Wang, Xiaoyu,Chen, Hong,Mallipeddi, Prema L.,Williams, Noelle S.,Posner, Bruce A.,Nijhawan, Deepak,Ready, Joseph M.
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p. 5199 - 5221
(2018/06/13)
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- Synthesis, antiproliferative and pro-apoptotic effects of nitrostyrenes and related compounds in Burkitt’s lymphoma
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Background: Cancers of the lymphatic cells (lymphomas) account for approximately 12% of malignant diseases worldwide. The nitrostyrene scaffold is identified as a lead target structure for the development of particularly effective compounds targeting Burkitt’s lymphoma (BL). Objectives: The aims of the curent study were to synthesise a panel of nitrostyrene compounds and to evaluate their activity in Burkitt’s lymphoma (BL). Methods: A panel of structurally varied compounds were designed and synthesised using Henry Knoevenagel condensation reactions. Single crystal X-Ray analysis confirmed the E configuration for six examples of these novel structures. A number of nitrostyrene-related compounds were also investigated including 1,3-bis(aryl)-2-nitropropenes together with heterocyclic scaffolds containing the nitrovinyl pharmacophore such as 3-nitro-2-phenyl-2H-chromenes. The antiproliferative activities of the compounds were evaluated using the BL cell lines EBV- MUTU-1 and EBV+ DG-75 (chemoresistant) to establish preliminary structure-activity relationships. Results: Lead compounds with optimized nitrostyrene scaffolds and 3-nitro-2-phenyl-2Hchromene structures were successfully established with typical IC50 values of 0.45 μM and 0.47 μM in MUTU-1 cells and 1.41 μM and 1.92 μM, respectively, in DG-75 cells. The mechanism of cell death was identified as apoptotic and the lead compound was found to elicit comparable apoptotic effects to Taxol in Burkitt’s lymphoma cell lines MUTU-1 and DG-75. Conclusion: This class of pharmaceutically active compounds with potential for the treatment of Burkitt’s lymphoma suggest a potential role for nitrostyrene based agents in chemotherapy.
- Byrne, Andrew J.,Bright, Sandra A.,Fayne, Darren,McKeown, James P.,McCabe, Thomas,Twamley, Brendan,Williams, Clive,Meegan, Mary J.
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p. 181 - 199
(2018/03/13)
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- Direct dihalo-alkoxylation of nitroalkenes leading to β,β-dihalo-β-nitroethyl alkyl ethers
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A highly efficient one-pot synthesis of β,β-dihalo-β-nitroethyl alkyl ethers is achieved by the treatment of nitroalkenes with alcohols and N-halosuccinimides in the presence of sodium hydride. The notable advantages of this protocol are that it involves simple experimental manipulations and tolerates a wide range of functional groups. Further transformations of the obtained ethers, such as allylation and conversion to β,β-dihalogenated vinyl ethers, are also investigated.
- Hao, Feiyue,Yokoyama, Soichi,Nishiwaki, Nagatoshi
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p. 2768 - 2775
(2018/04/26)
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- One-Step, Effective, and Cascade Syntheses of Highly Functionalized Cyclopentenes with High Diastereoselectivity
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Tetrabutylammonium fluoride works as an effective organocatalyst for the cycloaddition between phenacylmalononitriles and electron-deficient olefins (having substituent groups of NO2, CHO, and COR), providing a facile synthetic route to versatile multifunctionalized cyclopentenes having an allylic quaternary carbon center bearing both cyano and carboxamide groups with high yields and high diastereoselectivity. Preliminary studies reveal that these functionalized cyclopentenes are convenient precursors for making α-cyano-functionalized cyclopentadienone oximes.
- Alishetty, Suman,Shih, Hong-Pin,Han, Chien-Chung
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p. 2513 - 2516
(2018/05/17)
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- Electronic effect of substituents on anilines favors 1,4-addition to: Trans -β-nitrostyrenes: Access to N -substituted 3-arylindoles and 3-arylindoles
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A simple and an efficient method for the regioselective synthesis of N-alkyl/aryl/H 3-arylindole derivatives from N-substituted anilines and trans-β-nitrostyrenes has been described using 10 mol% of bismuth(iii) triflate as a catalyst in acetonitrile at 80 °C. The present protocol profits from the formation of new C-C and C-N bonds, broad substrate scope and moderate to good yields.
- Gattu, Radhakrishna,Bhattacharjee, Suchandra,Mahato, Karuna,Khan, Abu T.
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supporting information
p. 3760 - 3770
(2018/05/30)
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- Synthesis of nitroolefins and nitroarenes under mild conditions
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1,3-Disulfonic acid imidazolium nitrate {[Dsim]NO3} was prepared and characterized as a new ionic liquid and nitrating agent for the ipso-nitration of various arylboronic acids and nitro-Hunsdiecker reaction of different α,β-unsaturated acids and benzoic acid derivatives, by in situ generation of NO2 to give various nitroarenes and nitroolefins without using any cocatalysts and solvents under mild conditions.
- Zarei, Mahmoud,Noroozizadeh, Ehsan,Moosavi-Zare, Ahmad R.,Zolfigol, Mohammad A.
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p. 3645 - 3650
(2018/04/14)
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- tert-Butyl Nitrite Mediated Different Functionalizations of Internal Alkenes: Paths to Furoxans and Nitroalkenes
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tert-Butyl nitrite (TBN) reacts differently with various internal alkenes leading to interesting and useful products. Synthesis of 1,2,5-oxadiazole-N-oxides (furoxans) has been achieved from internal alkenes using tert-butyl nitrite (TBN), quinoline and K2S2O8. Under an identical reaction condition α,β-unsaturated carboxylic acids and cyclic and acyclic internal alkenes both afforded nitroalkenes as the sole product via decarboxylative and direct nitration path respectively. (Figure presented.).
- Mir, Bilal Ahmad,Singh, Sarangthem Joychandra,Kumar, Ritush,Patel, Bhisma K.
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p. 3801 - 3809
(2018/09/18)
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- Method for catalytically synthesizing (E)-beta-nitrostyrene derivatives based on tetraarylporphyrin iron
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The invention discloses a method for catalytically synthesizing (E)-beta-nitrostyrene derivatives based on tetraarylporphyrin iron. According to the method, styrene derivatives are subjected to one-pot reaction in a system containing tetraarylporphyrin iron (III), ammonium iodide and tert-butyl hydroperoxide to generate the (E)-beta-nitrostyrene derivatives. The method is capable of synthesizing beta-nitrostyrene derivatives with high E stereoselectivity with high yield under the mild reaction condition.
- -
-
Paragraph 0047; 0054-0056
(2017/08/31)
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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)
- -
-
Paragraph 0055-0058; 0065-0067
(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)
- -
-
Paragraph 0027; 0034; 0057; 0059; 0066; 0067; 0068
(2017/09/05)
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- High-selectivity (E)-beta-nitrostyrene derivative one-pot synthesizing method
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The invention discloses a high-selectivity (E)-beta-nitrostyrene derivative one-pot synthesizing method. In air or sealed environment, styrene derivative generates one-pot reaction in a system containing tetra-acryl ferroporphyrin (III), ammonium iodide and tert-butyl hydroperoxide to generate (E)-beta-nitrostyrene derivative. The method achieves the purpose of synthesizing the beta-nitrostyrene derivative with high E three-dimensional selectivity in high yield under moderate reaction conditions.
- -
-
Paragraph 0044-0048; 0055-0057
(2018/03/28)
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- Trans-4-methoxy-β-nitrostyrene relaxes rat thoracic aorta through a sGC-dependent pathway
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1-Nitro-2-phenylethene (NPe) induces a more potent vasorelaxant effect in rat aorta than its structural analog 1-nitro-2-phenylethane, but mediated through a different mechanism, independent of soluble guanylate cyclase (sGC) stimulation. We hypothesized
- Arruda-Barbosa, Loeste,Teófilo, Taylena Maria,Souza-Neto, Francisco das Chagas Vasconcelos,Duarte, Gloria Pinto,Vale, Joyce Karen Lima,Borges, Rosivaldo dos Santos,Magalh?es, Pedro Jorge Caldas,Lahlou, Saad
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p. 182 - 189
(2017/05/29)
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- Metal-free radical trifluoromethylation of β-nitroalkenes through visible-light photoredox catalysis
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A catalytic method for functional group interconversion is immensely important in modern sciences. Here, we report an efficient catalytic conversion of nitroalkenes to highly stereoselective 1-trifluoromethylalkenes at room temperature. This unprecedented metal-free photocatalytic strategy is simple and operates under visible-light irradiation using the commercially available CF3 source.
- Midya, Siba P.,Rana, Jagannath,Abraham, Thomas,Aswin, Bhaskaran,Balaraman, Ekambaram
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supporting information
p. 6760 - 6763
(2017/07/10)
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- A thiourea-functionalized metal-organic macrocycle for the catalysis of Michael additions and prominent size-selective effect
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A discrete tetranuclear thiourea-based metal-organic macrocycle (MOM) with a large size was constructed by a well-designed organic ligand and nickel(ii) ions via self-assembly. Incorporating thiourea groups as hydrogen-bond donors into a metal-organic com
- Yang, Lu,Zhao, Liang,Zhou, Zhen,He, Cheng,Sun, Hui,Duan, Chunying
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supporting information
p. 4086 - 4092
(2017/03/30)
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- Intermolecular [2+2] Photocycloaddition of β-Nitrostyrenes to Olefins upon Irradiation with Visible Light
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The title compounds were found to undergo a [2+2] photocycloaddition with olefins at λ = 419 nm in CH 2 Cl 2 as the solvent. The resulting cyclobutanes were isolated in yields of 32-87% (11 examples) and showed a defined relative configuration at C1/C4 in the major diastereoisomer (nitro and aryl trans). The analysis of side products and triplet sensitization experiments support a mechanistic scenario in which a 1,4-diradical is formed as a key intermediate.
- Mohr, Lisa-Marie,Bach, Thorsten
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supporting information
p. 2946 - 2950
(2017/12/14)
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- De novo endo-functionalized organic cages as cooperative multi-hydrogen-bond-donating catalysts
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Two endo-functionalized organic cages as oxyanion hole mimics were achieved via dynamic covalent chemistry, which exhibit good size selectivity, catalytic activity and broad substrate scopes for Friedel-Crafts reactions. The modular character of the synth
- Chen, Hong-Yu,Gou, Meng,Wang, Jiao-Bing
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supporting information
p. 3524 - 3526
(2017/03/31)
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- Chemoselective Henry Condensations Catalyzed by Artificial Carboligases
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The promiscuity of de novo designed enzymes provides a privileged platform for diverse abiological reactions. In this work, we report the first example of a nitroolefin synthase that catalyzes the Henry condensation between aromatic aldehydes and nitromethane. Significant catalytic activity was discovered in the computationally designed and evolved carboligase RA95.5-8, and mutations around the active site were shown to improve the reaction rate, demonstrating the potential to optimize the enzyme by directed evolution. This novel nitroolefin synthase could participate in complex biological cascades, whereby the highly tunable chemoselectivity could afford useful synthetic building blocks.
- Garrabou, Xavier,Macdonald, Duncan Stuart,Hilvert, Donald
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supporting information
p. 6001 - 6003
(2017/05/08)
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- Tetraarylphosphonium inner-salts (TAPIS) as both Lewis base catalyst and phase tag
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Tetraarylphosphonium inner-salts (TAPIS) have been designed, synthesized and verified as recyclable and reusable Lewis base catalysts. The resulted TAPIS catalyst has been successfully applied in Michael addition, cyanation and trifluoromethylation reactions.
- Guo, Shuhui,Mi, Xueling
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supporting information
p. 2881 - 2884
(2017/07/11)
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- Direct aziridination of nitroalkenes affording N-alkyl-C-nitroaziridines and the subsequent Lewis acid mediated isomerization to β-nitroenamines
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A mild and highly diastereoselective one-pot synthesis of trans-N-alkyl-C-nitroaziridines was achieved by treatment of nitroalkenes with aliphatic amines and N-chlorosuccinimide. Treatment of the obtained aziridines with a Lewis acid resulted in a facile ring opening reaction, accompanied by rearrangement and isomerization into functionalized (Z)-β-nitroenamines.
- Hao, Feiyue,Asahara, Haruyasu,Nishiwaki, Nagatoshi
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supporting information
p. 5442 - 5445
(2017/11/06)
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- Chloro/bromotrimethylsilane-Cu(NO3)2·3H2O: Safe and efficient reagent system for the decarboxylative ipso-nitration and dibromination of cinnamic acids
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Further synthetic potential of halotrimethylsilane-nitrate salt mixture is revealed. A mixture of TMSX-Cu(NO3)2·3H2O system is found to be an efficient reagent system for both the decarboxylative nitration (ipso-nitration) when X?=?Cl, and dibromination of cinnamic acids, with X?=?Br, under mild conditions. The reactions are safe and simple, affording the corresponding products (E)-β-nitrostyrenes, and anti-2,3-dibromo-3-phenylpropanoic acids in high yields with high selectivity in a relatively short time. Use of hazardous and toxic nitrating systems such as acetyl nitrate and brominating agents such as molecular bromine can be avoided.
- Roshandel, Sahar,Gurung, Laxman,Mathew, Thomas,Prakash, G.K. Surya
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supporting information
p. 2842 - 2845
(2017/06/27)
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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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- 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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- Iron-Mediated One-Pot Synthesis of 3,5-Diarylpyridines from β-Nitrostyrenes
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An operationally simple and mild one-pot protocol for the synthesis of a variety of 3,5-diarylpyridines from β-nitrostyrenes was achieved by using elemental iron. This reaction proceeds via reduction of the nitro group, resulting in in situ imine formation followed by trimolecular condensation with concomitant debenzylative aromatization. By employing this method, a series of symmetrical and unsymmetrical 3,5-diarylpyridines were synthesized with good to excellent yields. In addition, this method was also utilized for the synthesis of Sch-21418, an anti-inflammatory agent on gram scale.
- Sathish, Manda,Chetna, Jadala,Hari Krishna, Namballa,Shankaraiah, Nagula,Alarifi, Abdullah,Kamal, Ahmed
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p. 2159 - 2165
(2016/03/15)
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- Silver(I)-catalyzed denitrative trifluoromethylation of β-nitrostyrenes with CF3SO2Na
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A novel and convenient approach to the synthesis of substituted β-trifluoromethyl styrenes via a silver(I)-catalyzed denitrative trifluoromethylation with CF3SO2Na under relatively mild conditions has been developed. This protocol delivered excellent stereoselectivity and showed wide substrate tolerance.
- Huang, Ping,Li, Yaming,Fu, Xinmei,Zhang, Rong,Jin, Kun,Wang, Wenxin,Duan, Chunying
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supporting information
p. 4705 - 4708
(2016/10/03)
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- Organocatalytic Enantioselective Transfer Hydrogenation of β-Amino Nitroolefins
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The asymmetric organocatalytic transfer hydrogenation of β-acylamino and β-tert-butyloxycarbonylamino nitroolefins has been successfully realised in excellent enantioselectivities and yields (up to >99% ee, 97% yield) with a simple thiourea catalyst and a Hantzsch ester as hydrogen source, giving a direct access to enantiomerically pure β-amino nitroalkanes. (Figure presented.).
- Ferraro, Antonino,Bernardi, Luca,Fochi, Mariafrancesca
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supporting information
p. 1561 - 1565
(2016/10/13)
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- Cu(NO3)2-catalyzed nitrodecarboxylation of α,β-unsaturated acids: facile synthesis of (E)-nitroolefins under additive-free conditions
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Abstract: An additive-free, facile, efficient, and ecofriendly protocol for synthesis of (E)-nitroolefins via nitrodecarboxylation of α,β-unsaturated acids has been developed. Cu(NO3)2 was used as both nitrating agent and catalyst. Furthermore, the presented methodology offers several advantages such as easily accessible and stable substrates, inexpensive catalyst, high to excellent yield, short reaction time, and simple posttreatment procedure. Graphical Abstract: [Figure not available: see fulltext.]
- Luo, Zai-Gang,Xu, Feng,Fang, Yu-Yu,Liu, Peng,Xu, Xue-Mei,Feng, Cheng-Tao,Li, Zhong,He, Jie
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p. 6079 - 6087
(2016/06/01)
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- Cinchona alkaloid and di-: Tert -butyldicarbonate-DMAP promoted efficient synthesis of (E)-nitroolefins
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The synthesis of nitroolefins from aldehydes and olefins is generally limited by the formation of a mixture of cis and trans compounds. Here we report an alternative, metal-free protocol for the synthesis of β-nitroolefins from arylidinemalononitrile using cinchona alkaloid along with di-tert-butyldicarbonate-DMAP in high yields with total selectivity.
- Poomathi, Nataraj,Perumal, Paramasivan T.
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p. 54495 - 54502
(2016/07/06)
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