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Journal articles on the topic 'Nucleophilie'

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1

Tumanov, Vasily V, Alexander A Tishkov, and Herbert Mayr. "Nucleophilie-Parameter von Alkyl- und Arylisocyaniden." Angewandte Chemie 119, no. 19 (2007): 3633–36. http://dx.doi.org/10.1002/ange.200605205.

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2

Tsuji, Yutaka, and John P. Richard. "Swain–Scott relationships for nucleophile addition to ring-substituted phenonium ions." Canadian Journal of Chemistry 93, no. 4 (2015): 428–34. http://dx.doi.org/10.1139/cjc-2014-0337.

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The products of the reactions of 2-(4-methoxyphenyl)ethyl tosylate (MeO-1-OTs) and 2-(4-methyphenyl)ethyl tosylate (Me-1-OTs) with nucleophilic anions were determined for reactions in 50:50 (v/v) trifluoroethanol (TFE) / water at 25 °C. In many cases, the nucleophile selectivity kNu/ks ((mol/L)−1) for reactions of nucleophile and solvent, calculated from the ratio of product yields, depends upon [Nu−]. This demonstrates the existence of competing reaction pathways, which show different selectivities for reactions with nucleophiles. A 13C NMR analysis of the products of the reactions of substra
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3

Barham, Joshua P., Matthew P. John, and John A. Murphy. "One-pot functionalisation of N-substituted tetrahydroisoquinolines by photooxidation and tunable organometallic trapping of iminium intermediates." Beilstein Journal of Organic Chemistry 10 (December 12, 2014): 2981–88. http://dx.doi.org/10.3762/bjoc.10.316.

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Nucleophilic trapping of iminium salts generated via oxidative functionalisation of tertiary amines is well established with stabilised carbon nucleophiles. The few reports of organometallic additions have limited scope of substrate and organometallic nucleophile. We report a novel, one-pot methodology that functionalises N-substituted tetrahydroisoquinolines by visible light-assisted photooxidation, followed by trapping of the resultant iminium ions with organometallic nucleophiles. This affords 1,2-disubstituted tetrahydroisoquinolines in moderate to excellent yields.
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4

Yuasa, Hideya, Yujiro Kamata, and Hironobu Hashimoto. "Relative Nucleophilie der beiden Schwefelatome in 1,5-Dithioglucopyranosiden." Angewandte Chemie 109, no. 8 (1997): 907–9. http://dx.doi.org/10.1002/ange.19971090825.

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5

Yamashita, Makoto. "Nucleophilie des Borzentrums in Base-stabilisierten Borol-Anionen." Angewandte Chemie 122, no. 14 (2010): 2524–26. http://dx.doi.org/10.1002/ange.201000386.

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6

Phan, Thanh Binh, Martin Breugst, and Herbert Mayr. "Auf dem Weg zu einer allgemeinen Nucleophilie-Skala?" Angewandte Chemie 118, no. 23 (2006): 3954–59. http://dx.doi.org/10.1002/ange.200600542.

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7

Friedrich, Jens. "Einfluß von Nucleophilie und Basizität bei Additions- und Substitutionsreaktionen." CHEMKON 4, no. 4 (1997): 187–93. http://dx.doi.org/10.1002/ckon.19970040406.

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8

Selimović, Enisa, and Tanja Soldatović. "Study on the reactions between dichlorido[2,2′:6′,2″-terpyridine] zinc(II) and biologically relevant nucleophiles in aqueous solution." Progress in Reaction Kinetics and Mechanism 44, no. 2 (2019): 105–13. http://dx.doi.org/10.1177/1468678319825724.

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Substitution reactions of square-pyramidal [ZnCl2(terpy)] complex (terpy = 2,2′:6′,2″-terpyridine) with biologically relevant nucleophiles such as imidazole, glutathione, 1,2,4-triazole, and pyrazine were investigated at pH 7.0 as a function of nucleophile concentration. The reactions were followed under pseudo first-order conditions by UV-Vis spectrophotometry. The substitution reactions comprised two steps of consecutive displacement of chlorido ligands. Different reaction pathways for the first reaction step of nucleophilic substitution were defined. The order of reactivity of the investiga
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9

Um, Ik-Hwan, Ji-Youn Lee, Sun-Young Bae та Erwin Buncel. "Effect of modification of the electrophilic center on the α effect". Canadian Journal of Chemistry 83, № 9 (2005): 1365–71. http://dx.doi.org/10.1139/v05-157.

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We report on a nucleophilic study of esters R-C(=X)-Y-Ar in which the electrophilic center has been modified by replacing O by S in the leaving group or carbonyl center: 4-nitrophenyl acetate (1), S-4-nitrophenyl thioacetate (2), 4-nitrophenyl benzoate (3), and O-4-nitrophenyl thionobenzoate (4). The studies include O– and S– nucleophiles as well as α nucleophiles in H2O at 25.0 ± 0.1 °C. The sulfur nucleophile (4-chlorothiophenoxide, 4-ClPhS–) exhibits significant enhanced reactivity for the reactions with thiol and thione esters 2 and 4 compared with their oxygen analogues 1 and 3. On the co
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10

Vilotijevic, Ivan, Markus Lange, and You Zi. "Latent (Pro)Nucleophiles in Enantioselective Lewis Base Catalyzed Allylic Substitutions." Synlett 31, no. 13 (2020): 1237–43. http://dx.doi.org/10.1055/s-0040-1707130.

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The use of latent nucleophiles, which are molecules that are not nucleophilic but can be activated to act as a nucleophile at an opportune time during the reaction, expands the scope of Lewis base catalyzed reactions. Here, we provide an overview of the concept and show examples of applications to N- and C-centered nucleophiles in allylic substitutions. N- and C-silyl compounds are superior latent (pro)nucleophiles in Lewis base catalyzed reactions with allylic fluorides in which the formation of the strong Si–F bond serves as the driving force for the reactions. The latent (pro)nucleophiles e
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11

Giese, Bernd, Renate Engelbrecht, and Ulrich Erfort. "Der Einfluß des Acetoxysubstituenten auf die Nucleophilie von Alkyl-Radikalen." Chemische Berichte 118, no. 3 (1985): 1289–93. http://dx.doi.org/10.1002/cber.19851180345.

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12

Mayr, Herbert, and Matthias Patz. "Nucleophilie- und Elektrophilieskalen als Ordnungsprinzipien polarer organischer und metallorganischer Reaktionen." Angewandte Chemie 106, no. 9 (1994): 990–1010. http://dx.doi.org/10.1002/ange.19941060905.

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13

Mayer, Robert J., and Armin R. Ofial. "Nucleophilie von Glutathion als Bindeglied zur Reaktivität von Michael‐Akzeptoren." Angewandte Chemie 131, no. 49 (2019): 17868–72. http://dx.doi.org/10.1002/ange.201909803.

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14

Sheyi, Rotimi, Anamika Sharma, Ayman El-Faham, Beatriz G. de la Torre, and Fernando Albericio. "Phenol as a Modulator in the Chemical Reactivity of 2,4,6-Trichloro-1,3,5-triazine: Rules of the Game II." Australian Journal of Chemistry 73, no. 4 (2020): 352. http://dx.doi.org/10.1071/ch19524.

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2,4,6-Trichloro-1,3,5-triazine (TCT) is a privileged core that has the capacity to undergo sequential nucleophilic substitution reactions. Three nucleophiles, namely phenol, thiol and amine, were studied and the preferential order of incorporation on TCT was found to be first phenol, second thiol and third amine. The introduction of phenol was achieved at −20°C. The incorporation of this nucleophile in TCT helped to replace the third ‘Cl’ at 35°C, which is compatible with a biological context. The atomic charges on ‘Cl’ calculated by theoretical approaches were consistent with the experimental
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15

Mayer, Robert J., Takahiro Tokuyasu, Peter Mayer, et al. "Solvatation als Ursache für die unerwartete Nucleophilie-Reihung von Peroxid-Anionen." Angewandte Chemie 129, no. 43 (2017): 13463–67. http://dx.doi.org/10.1002/ange.201707086.

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16

Eom, Ga-eul, and Seokhee Kim. "Identification of Nucleophilic Probes for Protease-Mediated Transpeptidation." Molecules 23, no. 9 (2018): 2109. http://dx.doi.org/10.3390/molecules23092109.

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Proteases have evolved to mediate the hydrolysis of peptide bonds but may perform transpeptidation in the presence of a proper nucleophilic molecule that can effectively compete with water to react with the acyl-enzyme intermediate. There have been several examples of protease-mediated transpeptidation, but they are generally inefficient, and little effort has been made to systematically control the transpeptidation activity of other proteases with good nucleophiles. Here, we developed an on-bead screening approach to find a probe that functions efficiently as a nucleophile in the protease-med
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17

Dust, Julian M., and Richard A. Manderville. "Carbon versus oxygen nucleophilic selectivity in the reaction of the aryloxide ions, 2,6- and 3,5-di-tert-butylphenoxide, with the 2-[(nitro)\dn6 xaryl]-4,6-dinitrobenzotriazole 1-oxide series of super-electrophiles. Stereoelectronic factors on C-7 Meisenheimer complex formation versus C-1' SNAr displacement." Canadian Journal of Chemistry 76, no. 6 (1998): 662–71. http://dx.doi.org/10.1139/v98-028.

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The 2-[(nitro)xaryl]-4,6-dinitrobenzotriazole 1-oxides (1, Pi-DNBT (x = 3); 2, DNP-DNBT (x = 2); 3, NP-DNBT (x = 1)) are electron-deficient nitro-substituted heteroaromatic substrates that possess two sites for nucleophilic attachment: C-7 and C-1'. Generally, attack at the super-electrophilic C-7 site yields spectroscopically observable anionic sigma -bonded adducts, whereas attack at C-1' leads to displacement products in an overall process of nucleophilic aromatic substitution (SNAr). To gain an understanding of the factors affecting C-1' versus C-7 attack by potentially ambident aryloxide
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18

Damas, Liliana, Rui M. B. Carrilho, Sandra C. C. Nunes, et al. "A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis- N -heterocycles: rationalization by electronic structure calculations." Royal Society Open Science 5, no. 9 (2018): 181140. http://dx.doi.org/10.1098/rsos.181140.

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An unprecedented palladium-catalysed sequential aminocarbonylation/cyclization synthetic strategy, using carbon monoxide and structurally different aliphatic diamines as N -nucleophiles, gives access, in one pot, to a new family of indole-based N -heterocyclic derivatives (hydropyrazinones, benzodiazepinones and hydroquinoxalines). Optimization of the reaction conditions towards double carbonylation ( P CO = 30 bar, T = 80°C, iodoindole/diamine ratio = 1 : 1.5, toluene as solvent) allowed the target cyclic products, which are formed in situ via intramolecular cyclization of the ketocarboxamide
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19

Maji, Biplab, Martin Breugst, and Herbert Mayr. "N-Heterocyclische Carbene: Organokatalysatoren mit mäßiger Nucleophilie, aber außerordentlich hoher Lewis-Basizität." Angewandte Chemie 123, no. 30 (2011): 7047–52. http://dx.doi.org/10.1002/ange.201102435.

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20

Giese, Bernd, and Stephen Lachhein. "Addition von Alkyl-Radikalen an Alkine: Unterscheidung zwischen radikalischer und ionischer Nucleophilie." Angewandte Chemie 94, no. 10 (2006): 780–81. http://dx.doi.org/10.1002/ange.19820941006.

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21

Zhang, Yanbin, Ruiwen Jin, Guangxing Pan, and Hao Guo. "Light-enabled, AlCl3-catalyzed regioselective intramolecular nucleophilic addition of non-nucleophilic alkyls to alkynes." Chemical Communications 56, no. 78 (2020): 11621–24. http://dx.doi.org/10.1039/d0cc04636a.

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22

Sengee, Myagmarsuren, та Leiv K. Sydnes. "Specific conjugate addition to α,β-acetylenic ketones". Pure and Applied Chemistry 83, № 3 (2011): 587–96. http://dx.doi.org/10.1351/pac-con-10-10-24.

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A variety of α,β-unsaturated acetylenic ketones, prepared in good yields from 3,3,4,4-tetraethoxybut-1-yne (TEB), have been reacted with selected mono- and bis-nucleophilic reagents. The mononucleophiles react in a Michael fashion and give in most cases the corresponding α,β-unsaturated alkenones in good yield. Many of the alkenes are formed as single stereoisomers, but the configuration depends on the nature of the nucleophile. If hydrogen bonds can be formed, the Z geometry is preferred, otherwise the E geometry is completely predominant. Experiments have also uncovered that α,β-unsaturated
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23

Dust, Julian M., та Erwin Buncel. "Reactions of the super-electrophile, 2-(2′,4′-dinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide, with methoxide and tert-butoxide: basicity and steric hindrance as factors in σ-complex formation versus nucleophilic displacement". Canadian Journal of Chemistry 69, № 6 (1991): 978–86. http://dx.doi.org/10.1139/v91-143.

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The course of the reactions of methoxide and tert-butoxide with 2-(2′,4′-dinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide (4) clearly shows that the C-7 electrophilic site is significantly more reactive than the C-1′ site of the substrate. The reaction pathways of these alkoxides, which differ in basicity (as a measure of nucleophilicity) and steric bulk, were followed by 400 MHz 1H nuclear magnetic resonance spectroscopy. While both alkoxides lead to immediate formation of the respective C-7 anionic σ-adducts, a greater percentage of C-7 adduct formation occurs with methoxide as attacking nucl
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24

Crossley, Maxwell J., Lionel G. King, Simon M. Pyke, and Charles W. Tansey. "Reaction of 5-nitro-octaethylporphyrins with nucleophiles." Journal of Porphyrins and Phthalocyanines 06, no. 11 (2002): 685–94. http://dx.doi.org/10.1142/s1088424602000816.

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An investigation of the reactions of metallo-5-nitro-2,3,7,8,12,13,17,18-octaethylporphyrins with Grignard reagents, benzyl oxide, phenoxide and benzenethiolate nucleophiles shows that, except for benzenethiolate reactions, they are less efficient than related reactions of metallo-2-nitro-5,10,15,20-tetraarylporphyrins. Treatment of free-base and nickel(II) 5-nitro-octaethylporphyrin with the “soft” nucleophile benzenethiolate in DMF affords the corresponding 5-phenylthioporphyrins in 61 and 72% yield, respectively, by ipso-substitution of the nitro group. In contrast, with methylmagnesium iod
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25

Sugimoto, Takashi, and Wolfgang Pfleiderer. "Pteridines IC. Chemical Synthesis and Structural Proof of Photinuspterin." Pteridines 4, no. 1 (1993): 17–22. http://dx.doi.org/10.1515/pteridines.1993.4.1.17.

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SummaryThe proposed structure of Photinuspterin isolated from the firefly Photinus pyralis has been proven by two unambiguous syntheses to be 6-(1-hydroxypropyl)-8-methylisoxanthopteIin (15), 8-MethylisoxanthopteIin (7) can be substituted in 6-position in a homolytic nucleophilie substitution reaction either by the 1-hydroxypropyl radical to give 15 directly or by the propionyl radical leading first to 8-methyl-6-propionyl-isoxanthopteIin (9) which was easily converted into 15 by sodium borohydlide reduction. These two approaches are of general nature and can be applied to synthesize a broad v
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26

Fang, Yao-ren, Zhu-gen Lai, and Kenneth Charles Westaway. "Isotope effects in nucleophilic substitution reactions X. The effect of changing the nucleophilic atom on ion-pairing in an SN2 reaction." Canadian Journal of Chemistry 76, no. 6 (1998): 758–64. http://dx.doi.org/10.1139/v98-056.

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The effect of ion-pairing in an SN2 reaction is very different when the nucleophilic atom is changed from sulfur to oxygen, i.e., changing the nucleophile from thiophenoxide ion to phenoxide ion. When the nucleophile is sodium thiophenoxide, ion-pairing markedly alters the secondary α -deuterium kinetic isotope effect (transition state structure) and the substituent effect found by changing the para substituent on the nucleophile. When the nucleophile is sodium phenoxide, ion-pairing does not significantly affect the secondary α -deuterium or the chlorine leaving group kinetic isotope effects
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27

Yutilova, Kseniia, Yuliia Bespal’ko, and Elena Shved. "A Computational Study of 2-(chloromethyl)oxirane Ring Opening by Bromide and Acetate Anions Considering Electrophilic Activation with Cations of Alkali Metals." Croatica chemica acta 92, no. 3 (2019): 357–67. http://dx.doi.org/10.5562/cca3505.

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Ring opening of 2-(chloromethyl)oxirane via the nucleophilic substitution with bromide and acetate anions was investigated using density functional theory (DFT) calculations. It was shown that the geometry of the transition states and the activation parameters of the reactions correspond to those of SN2-like mechanism. The nature of localized transition states was analyzed using More O’Ferrall – Jencks plots. The quantum chemical simulations of the potential energy surface for the ring-opening reaction of oxirane by nucleophiles confirmed the theoretical assumptions about the favored path of i
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28

Carramiñana, Victor, Ana M. Ochoa de Retana, Francisco Palacios та Jesús M. de los Santos. "Synthesis of α-Aminophosphonic Acid Derivatives Through the Addition of O- and S-Nucleophiles to 2H-Azirines and Their Antiproliferative Effect on A549 Human Lung Adenocarcinoma Cells". Molecules 25, № 15 (2020): 3332. http://dx.doi.org/10.3390/molecules25153332.

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This work reports a straightforward regioselective synthetic methodology to prepare α-aminophosphine oxides and phosphonates through the addition of oxygen and sulfur nucleophiles to the C–N double bond of 2H-azirine derivatives. Determined by the nature of the nucleophile, different α-aminophosphorus compounds may be obtained. For instance, aliphatic alcohols such as methanol or ethanol afford α-aminophosphine oxide and phosphonate acetals after N–C3 ring opening of the intermediate aziridine. However, addition of 2,2,2-trifluoroethanol, phenols, substituted benzenthiols or ethanethiol to 2H-
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29

Zhang, Xiao, Guo-ping Lu, and Chun Cai. "Facile aromatic nucleophilic substitution (SNAr) reactions in ionic liquids: an electrophile–nucleophile dual activation by [Omim]Br for the reaction." Green Chemistry 18, no. 20 (2016): 5580–85. http://dx.doi.org/10.1039/c6gc01742h.

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30

Liljenberg, Magnus, Tore Brinck, Tobias Rein та Mats Svensson. "Utilizing the σ-complex stability for quantifying reactivity in nucleophilic substitution of aromatic fluorides". Beilstein Journal of Organic Chemistry 9 (23 квітня 2013): 791–99. http://dx.doi.org/10.3762/bjoc.9.90.

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A computational approach using density functional theory to compute the energies of the possible σ-complex reaction intermediates, the “σ-complex approach”, has been shown to be very useful in predicting regioselectivity, in electrophilic as well as nucleophilic aromatic substitution. In this article we give a short overview of the background for these investigations and the general requirements for predictive reactivity models for the pharmaceutical industry. We also present new results regarding the reaction rates and regioselectivities in nucleophilic substitution of fluorinated aromatics.
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31

Weiss, Robert, Matthias Handke, Silvia Reichel, and Frank Hampel. "Onio-assistierte SN2-Reaktionen: Allgemeiner Zugang zu symmetrischen und unsymmetrischen geminal bisoniosubstituierten Methanderivaten / Onio-Assisted SN2-Reactions: General Access to Symmetrical and Unsymmetrical Geminally Bisonio Substituted Methane Derivatives." Zeitschrift für Naturforschung B 53, no. 5-6 (1998): 599–619. http://dx.doi.org/10.1515/znb-1998-5-618.

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Abstract The arsonium salt [Ph3As-CH2-OTf]+ OTf- 11a contains a 1,1-biselectrophilic Csp3 center which permits to synthesize a wide range of symmetrical and unsymmetrical geminally bisonio-substituted methane derivatives. With neutral nucleophiles INu under mild condi- tions a series of 1.1-bisonium salts [Ph3As-CH2-Nu]2+ 2OTf- 12-23 is obtained in good yields. Under more stringent conditions the triphenylarsonio function in these salts can also be mobilized as a nucleofuge in a subsequent SN-reaction with a second nucleophile | Nu’, yielding a series of novel unsymmetrical 1,1-bisonium salts
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32

Bakardjiev, Mário, Suzan El Anwar, Dmytro Bavol, Zdeňka Růžičková, and Bohumír Grűner. "Focus on Chemistry of the 10-Dioxane-nido-7,8-dicarba-undecahydrido Undecaborate Zwitterion; Exceptionally Easy Abstraction of Hydrogen Bridge and Double-Action Pathways Observed in Ring Cleavage Reactions with OH− as Nucleophile." Molecules 25, no. 4 (2020): 814. http://dx.doi.org/10.3390/molecules25040814.

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Ring cleavage of cyclic ether substituents attached to a boron cage via an oxonium oxygen atom are amongst the most versatile methods for conjoining boron closo-cages with organic functional groups. Here we focus on much less tackled chemistry of the 11-vertex zwitterionic compound [10-(O-(CH2-CH2)2O)-nido-7,8-C2B9H11] (1), which is the only known representative of cyclic ether substitution at nido-cages, and explore the scope for the use of this zwitterion 1 in reactions with various types of nucleophiles including bifunctional ones. Most of the nitrogen, oxygen, halogen, and sulphur nucleoph
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33

Kimura, Tsutomu. "Recent Advances in Magnesium Carbenoid Chemistry." Synthesis 49, no. 23 (2017): 5105–19. http://dx.doi.org/10.1055/s-0036-1590894.

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Magnesium carbenoids are a class of organomagnesium species possessing a halo group at the α-position. The reactions of magnesium carbenoids can be classified into the following three categories: nucleophilic reactions resembling Grignard reagents, electrophilic reactions resembling organic halides, and rearrangements resembling carbenes. This short review summarizes recent studies on magnesium carbenoids reported between 2010 and 2016, and milestone studies reported before 2010 according to the classification of the reactions into the aforementioned three categories.1 Introduction2 Structures
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34

McNeish, Joanne R., J. Scott Parent, and Ralph A. Whitney. "Halogenated poly(isobutylene-co-isoprene): influence of halogen leaving-group and polymer microstructure on chemical reactivity." Canadian Journal of Chemistry 91, no. 6 (2013): 420–27. http://dx.doi.org/10.1139/cjc-2013-0068.

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Brominated (BIIR) and chlorinated (CIIR) poly(isobutylene-co-isoprene) are commercially available materials commonly known as halobutyl rubbers. The effect of leaving-group ability on the reactivity of halogenated poly(isobutylene-co-isoprene) was studied to place iodobutyl rubber reactivity into context with these materials. The effect of microstructure on reactivity of existing commercial materials was studied through comparison to that of polymers containing rearranged halomethyl (r-CIIR, r-BIIR, and r-IIIR) microstructure (prepared from as-received BIIR). The effect of leaving group on bot
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35

Kolodiazhnyi, Oleg I. "Stereochemistry of electrophilic and nucleophilic substitutions at phosphorus." Pure and Applied Chemistry 91, no. 1 (2019): 43–57. http://dx.doi.org/10.1515/pac-2018-0807.

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Abstract Nucleophilic and electrophilic substitutions are the most often applied reactions in organophosphorus chemistry. They are closely interrelated, because in a reacting pair always one reagent is an electrophile, and another nucleophile. The reactions of electrophilic and nucleophilic substitutions at the phosphorus center proceed via the formation of a pentacoordinated intermediate. The mechanism of nucleophilic substitution involves the exchange of ligands in the pentacoordinate phosphorane intermediate, leading to the more stable stereomer under the thermodynamic control. Electrophili
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36

Nudelman, Norma Sbarbati, Cecilia E. Silvana Alvaro, Monica Savini, Viviana Nicotra, and Jeannette Yankelevich. "Effects of the Nucleophile Structure on the Mechanisms of Reaction of 1-Chloro-2,4-dinitrobenzene with Aromatic Amines in Aprotic Solvents." Collection of Czechoslovak Chemical Communications 64, no. 10 (1999): 1583–93. http://dx.doi.org/10.1135/cccc19991583.

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The kinetics of reactions of 1-chloro-2,4-dinitrobenzene with aniline and several substituted aromatic amines, B, in toluene shows a quadratic dependence of the second-order rate constant, kA, on [B], which is preserved even in the presence of increasing amounts of dimethylaniline, while the reaction with N-methylaniline shows a linear dependence of kA vs [B]. All these results are interpreted by the "dimer nucleophile" mechanism, and confirmed by the effects of a non-nucleophilic hydrogen bond acceptor tertiary amine which show the relevance of the structure of the nucleophile and the role of
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37

Keddie, Neil S., Pier Alexandre Champagne, Justine Desroches, Jean-François Paquin, and David O'Hagan. "Stereochemical outcomes of C–F activation reactions of benzyl fluoride." Beilstein Journal of Organic Chemistry 14 (January 9, 2018): 106–13. http://dx.doi.org/10.3762/bjoc.14.6.

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In recent years, the highly polar C–F bond has been utilised in activation chemistry despite its low reactivity to traditional nucleophiles, when compared to other C–X halogen bonds. Paquin’s group has reported extensive studies on the C–F activation of benzylic fluorides for nucleophilic substitutions and Friedel–Crafts reactions, using a range of hydrogen bond donors such as water, triols or hexafluoroisopropanol (HFIP) as the activators. This study examines the stereointegrity of the C–F activation reaction through the use of an enantiopure isotopomer of benzyl fluoride to identify whether
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38

Kočovský, Pavel, and Andrei V. Malkov. "Asymmetric synthesis: From transition metals to organocatalysis." Pure and Applied Chemistry 80, no. 5 (2008): 953–66. http://dx.doi.org/10.1351/pac200880050953.

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Umpolung in the allylation reaction is discussed with examples drawn from transition-metal-catalyzed allylic substitution (with the allylic unit acting as an electrophile) and Lewis base-catalyzed allylation of aldehydes with allyltrichlorosilane (with the allyl acting as a nucleophile). Iridium-catalyzed electrophilic allylation of O-nucleophiles has been employed in our new approach to C-nucleoside analogs, where the C-O bond (rather than C-C) was constructed stereospecifically. Variation of the absolute configuration in the starting segments allowed the synthesis of all four combinations of
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39

Kutschy, Peter, Pavol Kristian, Milan Dzurilla, Dušan Koščík, and Róbert Nádaskay. "Selectivity of nucleophilic addition to and substitution at isothiocyanatocarbonyl group. Reactions of 4-pentinoyl- and 2-(2-propinyl)-4-pentinoyl isothiocyanate with amines and methanol." Collection of Czechoslovak Chemical Communications 52, no. 4 (1987): 995–1005. http://dx.doi.org/10.1135/cccc19870995.

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4-Pentinoyl isothiocyanate reacts with primary and secondary amines by either nucleophilic addition to N=C=S group to yield the corresponding thioureas, or a nucleophilic substitution at the carbonyl group to give 4-pentinoic acid amides. The less nucleophilic diphenylamine reacts selectively to afford the product of nucleophilic addition only. 2-(2-Propinyl)-4-pentinoyl isothiocyanate, having a sterically hindered carbonyl group, furnished with primary amines a mixture of amides and thioureas, whereas the bulkier secondary amines react selectively to form thioureas only. Both isothiocyanates
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40

Oh, Young-Ho, Hyoju Choi, Chanho Park, Dong Wook Kim, and Sungyul Lee. "Harnessing Ionic Interactions and Hydrogen Bonding for Nucleophilic Fluorination." Molecules 25, no. 3 (2020): 721. http://dx.doi.org/10.3390/molecules25030721.

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We review recent works for nucleophilic fluorination of organic compounds in which the Coulombic interactions between ionic species and/or hydrogen bonding affect the outcome of the reaction. SN2 fluorination of aliphatic compounds promoted by ionic liquids is first discussed, focusing on the mechanistic features for reaction using alkali metal fluorides. The influence of the interplay of ionic liquid cation, anion, nucleophile and counter-cation is treated in detail. The role of ionic liquid as bifunctional (both electrophilic and nucleophilic) activator is envisaged. We also review the SNAr
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41

Purwono, Bambang, and Estiana E. P. Daruningsih. "NUCHLEOPHILIC SUBSTITUTION REACTION OF CYANIDE AND METHOXYDE IONS TO QUATERNARY MANNICH BASE FROM VANILLIN." Indonesian Journal of Chemistry 7, no. 1 (2010): 58–60. http://dx.doi.org/10.22146/ijc.21713.

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The nucleophilic substitution reaction to quaternary Mannich base from vanillin has been investigated. Mannich reaction to vanillin was carried out by refluxing mixture of vanillin, formaldehyde and dimethyl amine. Quaternary ammonium halide salt was obtained from reaction of Mannich vanillin base with methyl iodide in THF solvents and yielded 93.28%. Nucleophilic substituion to the halide salts with cyanide nucleophile produced 4-hidroxy-3-methoxy-5-(cyano)methylbenzaldehyde in 54.39% yield, with methoxyde ion obtained 4-hidroxy- 3-methoxy-5-(methoxy)-methyl-benzaldehide in 67.80% yield. The
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42

Purwono, Bambang, and Estiana R. P. Daruningsih. "NUCLEOPHILIC SUBSTITUTION REACTION OF CYANIDE AND METHOXYDE IONS TO QUATERNARY MANNICH BASE FROM VANILLIN." Indonesian Journal of Chemistry 5, no. 3 (2010): 203–6. http://dx.doi.org/10.22146/ijc.21789.

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The nucleophilic substitution reaction to quaternary Mannich base from vanillin has been investigated. Mannich reaction to vanillin was carried out by refluxing mixture of vanillin, formaldehyde and dimethyl amine. Quaternary ammonium halide salt was obtained from reaction of Mannich vanillin base with methyl iodide in THF solvents and yielded 93.28 %. Nucleophilic substituion to the halide salts with cyanide nucleophile produced 4-hidroxy-3-methoxy-5-(cyano)methylbenzaldehyde in 54.39% yield. Reaction with methoxyde ion yielded 4-hydroxy- 3-methoxy-5-(methoxy) -methylbenzaldehyde in 67.80% yi
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43

Hudson, R., N. P. Bizier, K. N. Esdale, and J. L. Katz. "Synthesis of indoles, benzofurans, and related heterocycles via an acetylene-activated SNAr/intramolecular cyclization cascade sequence in water or DMSO." Organic & Biomolecular Chemistry 13, no. 8 (2015): 2273–84. http://dx.doi.org/10.1039/c4ob02549k.

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The synthesis of 2-substituted indoles and benzofurans was achieved by nucleophilic aromatic substitution, followed by subsequent 5-endo-dig cyclization between the nucleophile and an ortho acetylene.
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44

Cassagne, Thierry, Henri-Jean Cristau, Gérard Delmas та ін. "Comparative Evaluation of Oxidising and Nucleophilic Properties of Some α-Nucleophiles". Journal of Chemical Research 2002, № 7 (2002): 336–38. http://dx.doi.org/10.3184/030823402103172194.

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Six α-nucleophiles were evaluated at pH = 8 in an aqueous methanolic solution for their oxidising power towards tetrahydrothiophene, and the nucleophilic properties towards paraoxon. MMPP and m-CPBA are the most versatile reagents and can act as nucleophiles as well as oxidising agents.
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45

Ajenjo, Javier, Martin Greenhall, Camillo Zarantonello, and Petr Beier. "Synthesis and nucleophilic aromatic substitution of 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzene." Beilstein Journal of Organic Chemistry 12 (February 3, 2016): 192–97. http://dx.doi.org/10.3762/bjoc.12.21.

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3-Fluoro-5-nitro-1-(pentafluorosulfanyl)benzene was prepared by three different ways: as a byproduct of direct fluorination of 1,2-bis(3-nitrophenyl)disulfane, by direct fluorination of 4-nitro-1-(pentafluorosulfanyl)benzene, and by fluorodenitration of 3,5-dinitro-1-(pentafluorosulfanyl)benzene. The title compound was subjected to a nucleophilic aromatic substitution of the fluorine atom with oxygen, sulfur and nitrogen nucleophiles affording novel (pentafluorosulfanyl)benzenes with 3,5-disubstitution pattern. Vicarious nucleophilic substitution of the title compound with carbon, oxygen, and
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46

Song, Wangze, Ming Li, Junnan He, Junhao Li, Kun Dong, and Yubin Zheng. "Copper-catalyzed tandem annulation/enol nucleophilic addition to access multisubstituted indoles." Organic & Biomolecular Chemistry 17, no. 10 (2019): 2663–69. http://dx.doi.org/10.1039/c9ob00181f.

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47

da Silva, Gabriel, Eric M. Kennedy, and Bogdan Z. Dlugogorski. "Nucleophilic Catalysis of Nitrosation: Relationship between Nitrosating Agent Equilibrium Constant and Catalyst Nucleophilicity." Journal of Chemical Research 2002, no. 12 (2002): 589–90. http://dx.doi.org/10.3184/030823402103171069.

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48

Gao, Yu-Qi, Yi Hou, Liming Zhu, et al. "Visible-light driven synthesis of polycyclic benzo[d][1,3]oxazocine from 2-aminochalcone." Chemical Communications 56, no. 49 (2020): 6739–42. http://dx.doi.org/10.1039/d0cc02416c.

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49

Arcadi, Antonio, Giancarlo Fabrizi, Andrea Fochetti, et al. "Palladium-catalyzed Tsuji–Trost-type reaction of benzofuran-2-ylmethyl acetates with nucleophiles." RSC Advances 11, no. 2 (2021): 909–17. http://dx.doi.org/10.1039/d0ra09601f.

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50

Aimi, Takahiro, Tomohiro Meguro, Akihiro Kobayashi, Takamitsu Hosoya, and Suguru Yoshida. "Nucleophilic transformations of azido-containing carbonyl compounds via protection of the azido group." Chemical Communications 57, no. 49 (2021): 6062–65. http://dx.doi.org/10.1039/d1cc01143j.

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