cas 34312-77-1, (E)-2-(2-Nitroethenyl)thiophene

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Nonlinear optical properties of novel thiophene derivatives: Experimental and ab initio time-dependent coupled perturbed Hartree-Fock studies
We report in this paper experimental and theoretical studies of the nonlinear optical properties of a new class of compounds which differ from traditional second-order molecules in the sense that a commonly used electron donor chromophore is replaced by a thiophene ring.The molecular second-order nonlinear optical coefficients, β, is determined by the electric field-induced second-harmonic generation technique, for 2-nitro-1-(2-thienyl)ethene and 4-nitro-1-(2-thienyl)-1,3-butadiene are, respectively, 1 and 3 times that of para-nitroaniline.Ab initio time-dependent coupled perturbed Hartree-Fock results are in agreement with the experimental findings.A Mulliken population analysis indicates that the sulfur atom in the thiophene ring acts as an electron donor.Both the experimental and the theoretical results confirm that a thiophene ring acts as an efficient donor, giving rise to highly efficient second-order nonlinear optical properties.We also show that with this type of chromophore one can use a thiophene oligomer, in place of a thiophene monomer, to amplify the nonlinearity.
Karna, Shashi P.,Zhang, Yue,Samoc, Marek,Prasad, P. N.,Reinhardt, Bruce A.,Dillard, Ann G.
p. 9984 - 9993
(1993)
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Rational design of cannabinoid type-1 receptor allosteric modulators: Org27569 and PSNCBAM-1 hybrids
Allosteric modulation offers an alternate approach to target the cannabinoid type-1 receptor (CB1) for therapeutic benefits. Examination of the two widely studied prototypic CB1 negative allosteric modulators (NAMs) Org27569 and PSNCBAM-1 revealed structural resemblance and similar structure–activity relationships (SARs). In silico docking and dynamics simulation studies using the crystal structure of CB1 co-bound with CP55,940 and Org27569 suggested that Org27569 and PSNCBAM-1 occupied the same binding pocket and several common interactions were present in both series with the CB1 receptor. A new scaffold was therefore designed by merging the key structural features from the two series and the hybrids retained these binding features in the in silico docking studies. In addition, one such hybrid displayed similar functions to Org27569 in dynamic simulations by preserving a key R2143.50-D3386.30 salt bridge and maintaining an antagonist-like Helix3-Helix6 interhelical distance. Based on these results, a series of hybrids were synthesized and assessed in calcium mobilization, [35S]GTPγS binding and cAMP assays. Several compounds displayed comparable potencies to Org27569 and PSNCBAM-1 in these assays. This work offers new insight of the SAR requirement at the allosteric site of the CB1 receptor and provides a new scaffold that can be optimized for the development of future CB1 allosteric modulators.
Nguyen, Thuy,Gamage, Thomas F.,Decker, Ann M.,Finlay, David B.,Langston, Tiffany L.,Barrus, Daniel,Glass, Michelle,Harris, Danni L.,Zhang, Yanan
(2021/05/26)

Palladium-Catalyzed Formal (3 + 2) Cycloaddition Reactions of 2-Nitro-1,3-enynes with Vinylaziridines, -epoxides, and -cyclopropanes
A two-step Pd-catalyzed (3 + 2) cycloaddition/HNO2 elimination reaction sequence has been developed to give novel cyclic 1,3-dien-5-yne systems from Pd-stabilized zwitterionic 1,3-dipoles and 2-nitro-1,3-enyne substrates. The process is highly atom-efficient and tolerates the reaction of 2-vinyloxirane, 1-tosyl-2-vinylaziridine, and diethyl 2-vinylcyclopropane-1,1-dicarboxylate derived 1,3-dipoles with a variety of 2-nitro-1,3-enyne substrates. The stereochemistry of the intermediate (3 + 2) cycloadducts was determined by single crystal X-ray analysis. Furthermore, a selective kinetic elimination of the cycloadduct with an antiperiplanar relationship between the NO2 group and the participating hydrogen was demonstrated, allowing for efficient isolation of a single diastereoisomer of the cycloadduct.
Drew, Melanie A.,Tague, Andrew J.,Richardson, Christopher,Pyne, Stephen G.,Hyland, Christopher J. T.
supporting information
p. 4635 - 4639
(2021/06/28)

Organocatalytic Asymmetric Synthesis of Aza-Spirooxindoles via Michael/Friedel-Crafts Cascade Reaction of 1,3-Nitroenynes and 3-Pyrrolyloxindoles
An asymmetric [3+3] cyclization of nitroenynes and 3-pyrrolyloxindoles has been realized with a chiral bifunctional squaramide catalyst. This Michael/Friedel-Crafts cascade strategy provides a facile and efficient access to enantioenriched polycyclic aza-spirooxindoles with 32-95% isolated yields and excellent stereocontrol under mild reaction conditions.
Ni, Qijian,Wang, Xuyang,Zeng, Da,Wu, Qianling,Song, Xiaoxiao
supporting information
p. 2273 - 2278
(2021/04/05)

Skeletally Tunable Seven-Membered-Ring Fused Pyrroles
We describe a copper-mediated method that enables the synthesis of seven-membered-ring fused pyrroles (7-mrFPs). The protocol proceeds via an in situ spiro-intermediate ring expansion and tolerates a library of 7-mrFP derivatives with a broad range of functional groups in a simple step with tangible parameters and substrate adaptations. These rare 7-mrFPs are now accessible on a millimolar scale, and selected examples exhibit high antioxidant activity.
Andreou, Dimitrios,Essien, Nsikak B.,Pubill-Ulldemolins, Cristina,Terzidis, Michael A.,Papadopoulos, Athanasios N.,Kostakis, George E.,Lykakis, Ioannis N.
supporting information
p. 6685 - 6690
(2021/09/11)

Catalytic Asymmetric Construction of Tertiary Carbon Centers Featuring an α-Difluoromethyl Group with CF2H-CH2-NH2as the "building Block"
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)

Exploiting the chiral ligands of bis(Imidazolinyl)-and bis(oxazolinyl)thiophenes—Synthesis and application in Cu-catalyzed friedel–crafts asymmetric alkylation
Five new C2-symmetric chiral ligands of 2,5-bis(imidazolinyl)thiophene (L1–L3) and 2,5-bis(oxazolinyl)thiophene (L4 and L5) were synthesized from thiophene-2,5-dicarboxylic acid (1) with enantiopure amino alcohols (4a–c) in excellent optical purity and chemical yield. The util-ity of these new chiral ligands for Friedel–Crafts asymmetric alkylation was explored. Subse-quently, the optimized tridentate ligand L5 and Cu(OTf)2 catalyst (15 mol%) in toluene for 48 h promoted Friedel–Crafts asymmetric alkylation in moderate to good yields (up to 76%) and with good enantioselectivity (up to 81% ee). The bis(oxazolinyl)thiophene ligands were more potent than bis(imidazolinyl)thiophene analogues for the asymmetric induction of the Friedel–Crafts asymmetric alkylation.
Al-Majid, Abdullah Mohammed,Alammari, Abdullah Saleh,Alshahrani, Saeed,Barakat, Assem,Haukka, Matti,Islam, Mohammad Shahidul
(2021/12/17)

One-pot and metal-free synthesis of 3-arylated-4-nitrophenols via polyfunctionalized cyclohexanones from β-nitrostyrenes
β-Nitrostyrenes underwent a Diels-Alder reaction with Danishefsky's diene to afford cyclohexenes together with the corresponding hydrolyzed products, 3-arylated-5-methoxy-4-nitrocyclohexanones. When the reaction was conducted in the presence of water, the cyclohexenes were efficiently hydrolyzed into cyclohexanones. Subsequent aromatization by heating the cyclohexanone with a catalytic amount of iodine in dimethyl sulfoxide gave 3-arylated-4-nitrophenols. The reaction of nitrostyrenes with Danishefsky's diene could be conducted in one pot to directly afford the corresponding nitrophenols. Moreover, a heteroaryl group, e.g., a thienyl group could be introduced into the nitrophenol framework.
Asahara, Haruyasu,Hiraishi, Minami,Nishiwaki, Nagatoshi
p. 1830 - 1836
(2020/09/15)

Iodolopyrazolium Salts: Synthesis, Derivatizations, and Applications
The synthesis of iodolopyrazolium triflates via an oxidative cyclization of 3-(2-iodophenyl)-1H-pyrazoles is described. The reaction is characterized by a broad substrate scope, and various applications of these novel cyclic iodolium salts acting as useful synthetic intermediates are demonstrated, in particular in site-selective ring openings. This was finally applied to generate derivatives of the anti-inflammatory drug celecoxib. Their application as highly active halogen-bond donors is shown as well.
Boelke, Andreas,Caspers, Lucien D.,Kuczmera, Thomas J.,Lork, Enno,Nachtsheim, Boris J.
supporting information
p. 7261 - 7266
(2020/10/05)

Geometrically Selective Denitrative Trifluoromethylthiolation of β-Nitrostyrenes with AgSCF3for (E)-Vinyl Trifluoromethyl Thioethers
An efficient copper(II)-promoted denitrative trifluoromethylthiolation under mild reaction conditions has been developed for vinyl trifluoromethyl thioethers to construct Cvinyl-SCF3 bonds with stable AgSCF3 as a source of the trifluoromethylthio. This reaction system tolerates a broad range of functional groups to commendably achieve a high product yield and excellent stereoselectivity of E/Z.
Fang, Ge,Hong, Jianquan,Huang, Shuai,Jiang, Chao,Liu, Yang,Zhang, Wei,Zheng, Changge
supporting information

(2020/07/03)

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
supporting information

(2020/02/18)

NCC Pincer Ni (II) Complexes Catalyzed Hydrophosphination of Nitroalkenes with Diphenylphosphine
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
(2020/08/21)

A Nickel-Bisdiamine Porous Organic Polymer as Heterogeneous Chiral Catalyst for Asymmetric Michael Addition to Aliphatic Nitroalkenes
We report a polystyrene-incorporated chiral nickel(II)-bisdiamine complex, which is accessible on gram-scale. This metal complex functions as a heterogeneous catalyst for the enantioselective Michael addition between malonates and aliphatic nitroalkenes,
Buendia, Mikkel B.,Kegn?s, S?ren,Kramer, S?ren
supporting information
p. 5506 - 5512
(2020/10/23)

Facile Synthesis of 1,3,5-Triarylbenzenes and 4-Aryl-NH-1,2,3-Triazoles Using Mesoporous Pd-MCM-41 as Reusable Catalyst
We report mesoporous nano-Pd-MCM-41 catalyzed rapid and efficient synthesis of 1,3,5-triarylbenzenes via de-nitrative cyclotrimerization of β-nitrostyrenes. All the reactions were very fast and high yielding. The Pd-MCM-41 was also very effective in catalyzing de-nitrative [3+2] cycloaddition of β-nitrostyrenes with TMSN3 to synthesize 4-aryl-NH-1,2,3-triazoles. The catalyst was reused at least up to eight times with minimum loss of catalytic activity.
Saha, Arijit,Wu, Chia-Ming,Peng, Rui,Koodali, Ranjit,Banerjee, Subhash
p. 104 - 111
(2019/01/04)

Substrate promiscuity of ortho-naphthoquinone catalyst: Catalytic aerobic amine oxidation protocols to deaminative cross-coupling and n-nitrosation
ortho-Naphthoquinone-based organocatalysts have been identified as versatile aerobic oxidation catalysts. Primary amines were readily cross-coupled with primary nitroalkanes via deaminative pathway to give nitroalkene derivatives in good to excellent yields. Secondary and tertiary amines were inert to ortho-naphthoquinone catalysts; however, secondary nitroalkanes were readily converted by ortho-naphthoquinone catalysts to the corresponding nitrite species that in situ oxidized the amines to the corresponding N-nitroso compounds. Without using harsh oxidants in a stoichiometric amount, the present catalytic aerobic oxidation protocol utilizes the substrate promiscuity feature to provide a facile access to amine oxidation products under mild reaction conditions.
Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
p. 9216 - 9221
(2019/10/08)

A chiral bicyclic skeleton-tethered bipyridine-Zn(OTf)2 complex as a Lewis acid: Enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes
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
p. 4077 - 4086
(2019/04/30)

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.
supporting information
p. 347 - 353
(2019/01/10)

Base-catalyzed reactions enhanced by solid acids: Amine-catalyzed nitroaldol (Henry) reactions enhanced by silica gel or mesoporous silica SBA-15
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)

Squaramide-Linked Chloramphenicol Base Hybrid Catalysts for the Asymmetric Michael Addition of 2,3-Dihydrobenzofuran-2-carboxylates to Nitroolefins
An array of hybrid catalysts incorporating a chloramphenicol base moiety linked to another chiral scaffold through a squaramide linker were developed and successfully used in the Michael addition of 2,3-dihydrobenzofuran-2-carboxylates to nitroolefins. Control experiments suggested that the hybrid catalysts were more reactive than nonhybridized bifunctional catalysts, and matching of the chirality between the two scaffolds was crucial for high reactivity and stereoselectivity. These hybrid organocatalysts could be used with a variety of substrates. At a 0.5 mol-% catalyst loading, a range of 2,3-dihydrobenzofuran-2-carboxylates derivatives bearing quaternary and tertiary stereogenic centers were obtained in high yields (up to 98 %) with excellent enantioselectivities (up to 99 % ee) and moderate diastereoselectivities (up to 8:92 dr).
Yan, Linjie,Huang, Guanxin,Wang, Haifeng,Xiong, Fangjun,Peng, Haihui,Chen, Fener
supporting information
p. 99 - 103
(2018/01/17)

Synthesis of Benzo[4,5]imidazo[2,1-b]thiazole by Copper(II)-Catalyzed Thioamination of Nitroalkene with 1H-Benzo[d]imidazole-2-thiol
A Copper(II)-catalyzed thioamination of β-nitroalkene with 1H-benzo[d]imidazole-2-thiol has been developed for the synthesis of benzo[4,5]imidazo[2,1-b]thiazole derivatives. A variety of N-fused benzoimidazothiazole derivatives are obtained in high yields through successive C?N and C?S bond formations. This protocol is also applicable to β-substituted β-nitroalkenes to afford 2,3-disubstituted benzoimidazothiazoles. (Figure presented.).
Jana, Sourav,Chakraborty, Amrita,Shirinian, Valerii Z.,Hajra, Alakananda
supporting information
p. 2402 - 2408
(2018/05/08)

Synthesis, antiproliferative and pro-apoptotic effects of nitrostyrenes and related compounds in Burkitt’s lymphoma
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.
p. 181 - 199
(2018/03/13)

Enantioselective Conjugate Addition of 2-Acylimidazoles with Nitroalkenes Promoted by Chiral-at-Metal Rhodium(III) Complexes
An enantioselective conjugate addition of 2-acylimidazoles with nitroalkenes catalyzed by chiral-at-metal rhodium(III) complex under mild reaction conditions was developed, affording versatile γ-nitro ketone skeletons in good yields with excellent enantioselectivities (up to >99% ee). (Figure presented.).
Thota, Ganesh Kumar,Sun, Gui-Jun,Deng, Tao,Li, Yi,Kang, Qiang
supporting information
p. 1094 - 1098
(2018/01/22)

Direct dihalo-alkoxylation of nitroalkenes leading to β,β-dihalo-β-nitroethyl alkyl ethers
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
p. 2768 - 2775
(2018/04/26)

Electronic effect of substituents on anilines favors 1,4-addition to: Trans -β-nitrostyrenes: Access to N -substituted 3-arylindoles and 3-arylindoles
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.
supporting information
p. 3760 - 3770
(2018/05/30)

Highly Enantioselective Michael Addition of Dithiomalonates to Nitroolefins Catalyzed by New Bifunctional Chiral Thioureas
We report a highly efficient asymmetric Michael addition of dithiomalonates to trans -β-nitroole?ns catalyzed by versatile cinchona-based bifunctional thioureas, which provides the corresponding adducts in high yields (up to 92%) and with excellent enanti
Yuan, Jia-Ni,Liu, Hui-Xia,Tian, Qin-Qin,Ji, Nan,Shen, Kuo,He, Wei
supporting information
p. 2577 - 2586
(2018/05/03)

A Deprotonation Approach to the Unprecedented Amino-Trimethylenemethane Chemistry: Regio-, Diastereo-, and Enantioselective Synthesis of Complex Amino Cycles
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)

Drug application for benzene [g] ceteroary [a, g] quinazine compound and preparation method thereof
The invention relates to a new application of a benzene [g] ceteroary [a, g] quinazine compound and a preparation method thereof. Specifically, the invention relates to the application of the benzene [g] ceteroary [a, g] quinazine compound in preparing the drug for treating and/or preventing the metabolic diseases caused by AMPK route, especially, the diabetes, adiposis, fatty liver and complication thereof caused by insulin resistance.
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Paragraph 0107; 0108

(2017/11/16)

Catalyst-free sulfa-Michael addition of pyrimidine-2-thiol to nitroolefins
Catalyst-free sulfa-Michael addition of pyrimidine-2-thiol to nitroolefins is described. A series of 2-((2-nitro-1-arylethyl)thio)pyrimidines were efficiently synthesized. The protocol has advantages of wide range of substituents tolerance, no catalyst, additives and bases, mild condition, and high yield. The method can also extend to gram scale.
Li, Zheng,Song, Geyang,He, Jiaojiao,Du, Yan,Yang, Jingya
p. 686 - 698
(2017/09/06)

Continuous-flow synthesis using a column reactor packed with heterogeneous catalysts: A convenient production of nitroolefins by using amino-functionalized silicagel
A continuous-flow synthesis of β-nitroolefins by using heterogeneous base catalysts has been developed. Although the use of an excess amount of nitro-donor such as nitromethane is required in conventional methods, nearly equimolar amounts of nitro-donors and carbonyl compounds are sufficient for high-yielding production of nitroolefins. Catalysts for this flow protocol are inexpensive and abundant, and high durability and high productivity were also realized by using an appropriate second support.
Ishitani, Haruro,Furiya, Yuichi,Kobayashi, Shū
supporting information
p. 6229 - 6232
(2017/09/30)

Cyanide-Free and Broadly Applicable Enantioselective Synthetic Platform for Chiral Nitriles through a Biocatalytic Approach
A cyanide-free platform technology for the synthesis of chiral nitriles by biocatalytic enantioselective dehydration of a wide range of aldoximes is reported. The nitriles were obtained with high enantiomeric excess of >90 % ee (and up to 99 % ee) in many cases, and a “privileged substrate structure” with respect to high enantioselectivity was identified. Furthermore, a surprising phenomenon was observed for the enantiospecificity that is usually not observed in enzyme catalysis. Depending on whether the E or Z isomer of the racemic aldoxime substrate was employed, one or the other enantiomer of the corresponding nitrile was formed preferentially with the same enzyme.
Betke, Tobias,Rommelmann, Philipp,Oike, Keiko,Asano, Yasuhisa,Gr?ger, Harald
supporting information
p. 12361 - 12366
(2017/09/06)

Palladium-Catalyzed Intramolecular Cyclization of Nitroalkenes: Synthesis of Thienopyrroles
In the presence of carbon monoxide, the palladium/phenanthroline system catalyzes the intramolecular amination of thiophene rings following the reduction of a nitroalkene moiety directly attached to the S-heterocyclic ring. Optimization of the ligand and reaction conditions allowed the synthesis of a series of thienopyrroles aryl/alkyl-substituted at either the 2- or 3-position of the pyrrole ring. By using low pressures of carbon monoxide (5 bars), high yields of fused bicyclic compounds have been obtained (up to 98 % yield).
El-Atawy, Mohamed A.,Ferretti, Francesco,Ragaini, Fabio
p. 1902 - 1910
(2017/04/21)

Intermolecular [2+2] Photocycloaddition of β-Nitrostyrenes to Olefins upon Irradiation with Visible Light
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
supporting information
p. 2946 - 2950
(2017/12/14)

Tetraarylphosphonium inner-salts (TAPIS) as both Lewis base catalyst and phase tag
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
supporting information
p. 2881 - 2884
(2017/07/11)

Metal-free radical trifluoromethylation of β-nitroalkenes through visible-light photoredox catalysis
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
supporting information
p. 6760 - 6763
(2017/07/10)

Direct aziridination of nitroalkenes affording N-alkyl-C-nitroaziridines and the subsequent Lewis acid mediated isomerization to β-nitroenamines
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
supporting information
p. 5442 - 5445
(2017/11/06)

In order to iodide is one pot synthesis nitryl source α, β - unsaturated nitro olefin derivatives (by machine translation)
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 0055-0058; 0113-0115

(2017/09/01)

Α, β - unsaturated nitro olefin derivative synthesis method (by machine translation)
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; 0057; 0059; 0114; 0115; 0116

(2017/09/05)

Fe(III)/Pyridine-Mediated Decarboxylative Nitration of α,β-Unsaturated Acids with Iron Nitrate
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
supporting information
p. 1079 - 1082
(2017/05/19)

Stereoselective Synthesis of Alkenyl Silanes, Sulfones, Phosphine Oxides, and Nitroolefins by Radical C-S Bond Cleavage of Arylalkenyl Sulfides
A radical-mediated approach has been introduced for the C-S bond activation of arylalkenyl sulfides. The protocol provides an efficient approach for the generation of various alkenes including alkenyl silanes, sulfones, phosphine oxides, and nitroolefins. In most cases, these radical substitutions are performed under metal-free conditions with stereospecificity.
Lin, Ya-mei,Lu, Guo-ping,Wang, Rong-kang,Yi, Wen-bin
p. 1100 - 1103
(2017/03/15)

An Asymmetric Vinylogous Michael Cascade of Silyl Glyoximide, Vinyl Grignard, and Nitroalkenes via Long Range Stereoinduction
A diastereoselective auxiliary-mediated vinylation/[1,2]-Brook rearrangement/vinylogous Michael cascade of silyl glyoximide, vinylmagnesium bromide, and nitroalkenes is described. The reaction occurs with complete regio- and diastereocontrol in good yield. The diastereoselectivity is induced by a rare instance of 1,7-chirality transfer that is hypothesized to arise from a trans-multihetero-decalin transition state. (Chemical Equation).
Boyce, Gregory R.,Johnson, Jeffrey S.
p. 1712 - 1717
(2016/03/01)

Synthesis method of ticlopidine hydrochloride drug intermediate 2-(2-nitrovinyl)thiophene
A synthesis method of ticlopidine hydrochloride drug intermediate 2-(2-nitrovinyl)thiophene comprises steps as follows: 1.3 mol of a thiophene methyl glycol solution, 1.6-1.9 mol of a nitromethane solution and 900 ml of hexane are added to a reaction container provided with a stirrer, a thermometer and a dropping funnel, the temperature of the solution is decreased to 3-7 DEG C, the stirring speed of the solution is controlled to range from 110 rpm to 130 rpm, a reaction is conducted for 4-7 h, the temperature of the solution is increased to 50-55 DEG C, 500 ml of a potassium bromide solution is added for a reaction for 3-5 h, 300 ml of an oxalic acid solution is added, the temperature of the solution is decreased to 10-16 DEG C, a reaction is conducted for 80-110 min, the temperature is decreased to 2-5 DEG C, the solution is left to stand for 5-7 h, solids separate out, are filtered, are washed with a saline solution, ethyl acetate and chlorobenzene, are dehydrated by the aid of a dehydrating agent and are recrystallized in dimethylbenzene, and crystal 2-(2-nitrovinyl)thiophene is obtained.
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Paragraph 0007; 0015; 0016

(2016/11/09)

K2S2O8-mediated nitration of alkenes with NaNO2 and 2,2,6,6-tetramethylpiperidine-1-oxyl: Stereoselective synthesis of (E)-nitroalkenes
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
supporting information
p. 80 - 84
(2015/12/23)

Synthesis of Heteroaryl-Substituted Pyrroles via the 1,3-Dipolar Cycloaddition of Unsymmetrical Münchnones and Nitrovinylheterocycles
A series of furanyl-, thiophenyl-, and pyrrolo-substituted pyrroles were prepared via the 1,3-dipolar cycloaddition of unsymmetrical münchnones and nitrovinylheterocycles. The regiochemical outcome of the furan and thiophene cycloadditions compares favorably to previously reported cycloadditions with β-nitrostyrene, while the nitrovinylpyrrole cycloadditions mirror the results observed with nitrovinylindole.
Lopchuk, Justin M.,Song, Mia,Butler, Blythe,Gribble, Gordon W.
p. 2776 - 2780
(2015/09/15)

DIARYL[A, G]QUINOLIZIDINE COMPOUND, PREPARATION METHOD THEREFOR, PHARMACEUTICAL COMPOSITION, AND USES THEREOF
The present invention relates to a diarylo[a,g]quinolizidine compound of formula (I), enantiomer, diastereoisomer, racemate, mixture, pharmaceutically acceptable salt, crystalline hydrate or solvate thereof; the preparation method thereof, and uses thereof in preparing an experimental model drugs related to dopamine receptors and 5-HT receptors or a medicament for treating or preventing a disease related to dopamine receptors and 5-HT receptors.
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Paragraph 0053; 0054

(2015/03/28)

DIARYL[A, G]QUINOLIZIDINE COMPOUND, PREPARATION METHOD THEREFOR, PHARMACEUTICAL COMPOSITION, AND USES THEREOF
The present invention relates to a diarylo[a,g]quinolizidine compound of formula (I), enantiomer, diastereoisomer, racemate, mixture, pharmaceutically acceptable salt, crystalline hydrate or solvate thereof; the preparation method thereof, and uses thereof in preparing an experimental model drugs related to dopamine receptors and 5-HT receptors or a medicament for treating or preventing a disease related to dopamine receptors and 5-HT receptors.
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Paragraph 0113; 0114

(2015/05/26)

Erratum: Correction to p -toluenesulfonic acid mediated 1,3-dipolar cycloaddition of nitroolefins with NaN3 for synthesis of 4-Aryl- NH -1,2,3-triazoles (Organic Letters (2014) 16:21 (5728-5731) DOI: 10.1021/ol5027975)
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Quan, Xue-Jing,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
supporting information
p. 393 - 393
(2015/01/30)

Direct fluorination of styrenes
We have developed a practical method to synthesize fluorostyrene compounds. A mild and regioselective mono-fluorination reaction occurred smoothly for various di- and trisubstituted styrenes in the presence of RuCl3 and N-fluorobenzenesulfonimide (NFSI). A tandem alkyne hydroarylation-olefin fluorination reaction was also developed using an Au catalyst.
Shao, Qian,Huang, Yong
supporting information
p. 6584 - 6586
(2015/04/14)

17a-HYDROXYLASE/C17,20-LYASE INHIBITORS
The present invention provides compounds of Formula (I), or a pharmaceutically acceptable salt thereof, where R1, R2, R3, R4, R5, R6, A and n are as defined herein. A deuteriated derivative of the compound of Formula (I) is also provided.
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Paragraph 0253; 0254

(2014/03/21)

A greener, efficient approach to michael addition of barbituric acid to nitroalkene in aqueous diethylamine medium
An efficient method for the synthesis of a variety of pyrimidine derivatives 3a-t by reaction of barbituric acids 1a,b as Michael donor with nitroalkenes 2a-k as Michael acceptor using an aqueous medium and diethylamine is described. This 1,4-Addition strategy offers several advantages, such as using an economic and environmentally benign reaction media, high yields, versatility, and shorter reaction times. The synthesized compounds were identified by 1H-NMR, 13C-NMR, CHN, IR, and MS. The structure of compound 3a was further confirmed by single crystal X-ray structure determination.
Al-Najjar, Hany J.,Barakat, Assem,Al-Majid, Abdullah M.,Mabkhot, Yahia N.,Weber, Manuel,Ghabbour, Hazem A.,Fun, Hoong-Kun
p. 1150 - 1162
(2014/02/14)

Useful extensions of the henry reaction: Expeditious routes to nitroalkanes and nitroalkenes in aqueous media
The products of the Henry nitroaldol reaction from nitromethane and several aldehydes were reduced to the corresponding nitroalkanes with (n-Bu) 3SnH in water under microwave irradiation (80 °C/10 min), or dehydrated to the corresponding nitroalkenes with K2CO3 in water (generally 0-5 °C/20 min). Both "one-pot" reactions occur in excellent yields across a range of aliphatic and aromatic (including heteroaromatic) substrates. It seems likely that the deoxygenation of the nitroaldols occurs via coordination of an oxygen atom of the nitro group with a tin atom, which facilitates hydride delivery in the transition state. The elimination of water from the nitroaldols in mild base is likely driven by the stability of the conjugated nitroalkene products. The elimination required workup with 2 N HCl, which likely displaces a nitroalkane-nitroalkene equilibrium towards the latter. These extensions of the Henry reaction lead to products not easily obtained otherwise.
Chandrasekhar, Sosale,Shrinidhi, Annadka
p. 3008 - 3018
(2014/10/16)

New approach to oximes through reduction of nitro compounds enabled by visible light photoredox catalysis
A range of nitro compounds are smoothly reduced to their corresponding oximes under the synergistic effects of visible light irradiation, the Ru(bpy)3Cl2 photocatalyst, Hünig's base, Mg(ClO 4)2 activation, and MeCN solvent. This remarkably mild and environmentally benign protocol, when orchestrated with classical Beckmann rearrangement, enables such high-value industrial feedstock as caprolactam to be readily accessed from simple precursor nitrocyclohexane.
Cai, Shunyou,Zhang, Shaolong,Zhao, Yaohong,Wang, David Zhigang
supporting information
p. 2660 - 2663
(2013/07/11)