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1

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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2

Szántay, Csaba, Álmos Gorka-Kereskényi, Lajos Szabó, et al. "Aromatic Electrophilic Substitutions on Vindoline." HETEROCYCLES 71, no. 7 (2007): 1553. http://dx.doi.org/10.3987/com-07-11049.

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3

Puciová, Monika, Eva Solčániová, and Štefan Toma. "Electrophilic substitutions on some ferrocenylheteroarenes." Tetrahedron 50, no. 19 (1994): 5765–74. http://dx.doi.org/10.1016/s0040-4020(01)85644-1.

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4

COOMBES, R. G. "ChemInform Abstract: Electrophilic Aromatic Substitutions." ChemInform 28, no. 30 (2010): no. http://dx.doi.org/10.1002/chin.199730259.

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5

Christoffers, Jens, and Mathias S. Wickleder. "Synthesis of Aromatic and Aliphatic Di-, Tri-, and Tetrasulfonic Acids." Synlett 31, no. 10 (2020): 945–52. http://dx.doi.org/10.1055/s-0039-1691745.

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Oligosulfonic acids are promising linker compounds for coordination polymers and metal-organic frameworks, however, compared to their carboxylic acid congeners, often not readily accessible by established synthetic routes. This Account highlights the synthesis of recently developed aromatic and aliphatic di-, tri- and tetrasulfonic acids. While multiple electrophilic sulfonations of aromatic substrates are rather limited, the nucleophilic aromatic substitution including an intramolecular variant, the Newman–Kwart rearrangement, allows the flexible introduction of up to four sulfur-containing m
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6

Uchida, Yuzuru, and Shigeru Oae. "Electrophilic Substitutions on Tris(Pyridyl)Phosphine." Phosphorus, Sulfur, and Silicon and the Related Elements 109, no. 1-4 (1996): 605–8. http://dx.doi.org/10.1080/10426509608545226.

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7

Gracza, Tibor, Zdeněk Arnold, and Jaroslav Kováč. "Electrophilic ipso substitutions of furan vinamidinium salts." Collection of Czechoslovak Chemical Communications 53, no. 5 (1988): 1053–59. http://dx.doi.org/10.1135/cccc19881053.

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5-(N,N-Dialkylamino)-2-furfurylidene-N,N-dialkylimminium salts I (the vinamidinium salts of furan) react with arenediazonium salts to give products of ipso substitution in position 2 of the furan ring, i.e. 5-(N,N-dialkylamino)-2-azoarenefuran salts II. The structure of these products was evidenced by 1H NMR and UV spectral data.
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8

Keumi, Takashi, Naoto Tomioka, Kozo Hamanaka, et al. "Positional reactivity of dibenzofuran in electrophilic substitutions." Journal of Organic Chemistry 56, no. 15 (1991): 4671–77. http://dx.doi.org/10.1021/jo00015a020.

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9

KNIPE, A. C. "ChemInform Abstract: Carbanions and Electrophilic Aliphatic Substitutions." ChemInform 28, no. 30 (2010): no. http://dx.doi.org/10.1002/chin.199730256.

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10

PUCIOVA, M., E. SOLCANIOVA, and S. TOMA. "ChemInform Abstract: Electrophilic Substitutions on Some Ferrocenylheteroarenes." ChemInform 25, no. 39 (2010): no. http://dx.doi.org/10.1002/chin.199439228.

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11

Hammond, Gerald B. "Nucleophilic and electrophilic substitutions of difluoropropargyl bromides." Journal of Fluorine Chemistry 127, no. 4-5 (2006): 476–88. http://dx.doi.org/10.1016/j.jfluchem.2005.12.024.

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12

Tanaka, Mutsuo. "ChemInform Abstract: Electrophilic Aromatic Substitutions Using Superacids." ChemInform 30, no. 45 (2010): no. http://dx.doi.org/10.1002/chin.199945319.

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13

Helmchen, G., Martin Ernst, and G. Paradies. "Application of allylic substitutions in natural products synthesis." Pure and Applied Chemistry 76, no. 3 (2004): 495–505. http://dx.doi.org/10.1351/pac200476030495.

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Synthesis routes are described, allowing all known jasmonoids as well as their enantiomers to be synthesized in enantiomerically and diastereomerically pure form. The routes are based on a set of closely related lactones containing an electrophilic allylic moiety, which are accessible via asymmetric Pd-catalyzed allylic alkylation. Regio- and diastereoselective SN2'-anti-reactions of the electrophilic lactones with organocopper compounds furnished 2,3-cis-disubstituted cyclopentenones, which were further transformed into the target compounds, i.e., 12-oxophytodienoic acid (12-OPDA) in excellen
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14

Tanaka, Mutsuo. "ChemInform Abstract: A New Aspect in Electrophilic Aromatic Substitutions: Intracomplex and Conventional Electrophilic Aromatic Substitutions in Gattermann-Koch Formylation." ChemInform 31, no. 24 (2010): no. http://dx.doi.org/10.1002/chin.200024250.

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15

Munárriz, Julen, Miguel Gallegos, Julia Contreras-García, and Ángel Martín Pendás. "Energetics of Electron Pairs in Electrophilic Aromatic Substitutions." Molecules 26, no. 2 (2021): 513. http://dx.doi.org/10.3390/molecules26020513.

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The interacting quantum atoms approach (IQA) as applied to the electron-pair exhaustive partition of real space induced by the electron localization function (ELF) is used to examine candidate energetic descriptors to rationalize substituent effects in simple electrophilic aromatic substitutions. It is first shown that inductive and mesomeric effects can be recognized from the decay mode of the aromatic valence bond basin populations with the distance to the substituent, and that the fluctuation of the population of adjacent bonds holds also regioselectivity information. With this, the kinetic
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16

D’Auria, Maurizio. "Electrophilic substitutions and HOMOs in azines and purines." Tetrahedron Letters 46, no. 37 (2005): 6333–36. http://dx.doi.org/10.1016/j.tetlet.2005.07.033.

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17

UCHIDA, Y., and S. OAE. "ChemInform Abstract: Electrophilic Substitutions on Tris(pyridyl)phosphine." ChemInform 28, no. 12 (2010): no. http://dx.doi.org/10.1002/chin.199712308.

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18

Zheng, Xinyuan, Fangyi Cao, Chao Wang, et al. "Expanding the hole delocalization range in excited molecules for stable organic light-emitting diodes employing thermally activated delayed fluorescence." Journal of Materials Chemistry C 8, no. 29 (2020): 10021–30. http://dx.doi.org/10.1039/d0tc01897j.

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The degradation in TADF OLEDs is found to be governed by the radical electrophilic substitutions between two charge-transfer (CT) excitons. Expanding the mean localization distance (RLOL) of hole in the CT state can improve device stability.
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19

Mendoza-Huizar, Luis, Clara Rios-Reyes, and Hector Zuñiga-Trejo. "A computational study of the chemical reactivity of isoxaflutole herbicide and its active metabolite using global and local descriptors." Journal of the Serbian Chemical Society 85, no. 9 (2020): 1163–74. http://dx.doi.org/10.2298/jsc191105024m.

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In this work, the chemical reactivity of isoxaflutole (ISOX) and diketonitrile (DKN) was analyzed at the X/6-311++G(2d,2p) (where X = = B3LYP, M06, M06L and ?B97XD) level of theory, in the gas and aqueous phases. The results indicate that DKN, the active metabolite of ISOX, is more stable than isoxaflutole in both phases. ISOX is susceptible to electrophilic and free radical reactions through the isoxazole ring; while the carbonyl group is attacked by nucleophiles. For DKN nucleophilic and free radical attacks are expected on the aromatic ring, while electrophilic attacks are favored on the ox
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20

Do, Quang Tho, Driss Elothmani, and Georges Le Guillanton. "Electrophilic substitutions with the electrogenerated sulfenium cation R1-S+." Tetrahedron Letters 39, no. 26 (1998): 4657–58. http://dx.doi.org/10.1016/s0040-4039(98)00871-5.

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21

KEIMI, T., N. TOMIOKA, K. HAMANAKA, et al. "ChemInform Abstract: Positional Reactivity of Dibenzofuran in Electrophilic Substitutions." ChemInform 22, no. 52 (2010): no. http://dx.doi.org/10.1002/chin.199152169.

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22

KACHURIN, O. I., A. P. ZARAISKII, L. I. VELICHKO, N. A. ZARAISKAYA, N. M. MATVIENKO, and Z. A. OKHRIMENKO. "ChemInform Abstract: Phase-Transfer Catalysis in Electrophilic Aromatic Substitutions." ChemInform 27, no. 8 (2010): no. http://dx.doi.org/10.1002/chin.199608320.

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23

Güllük, Eduard, Elena Bogdan, and Manfred Christl. "3-Substituted Cyclopenta[c]pyrans: Synthesis and Electrophilic Substitutions." European Journal of Organic Chemistry 2006, no. 2 (2006): 531–42. http://dx.doi.org/10.1002/ejoc.200500631.

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24

Gorbunova, Tatyana I., Julia O. Subbotina, Viktor I. Saloutin, and Oleg N. Chupakhin. "Reactivity of polychlorinated biphenyls in nucleophilic and electrophilic substitutions." Journal of Hazardous Materials 278 (August 2014): 491–99. http://dx.doi.org/10.1016/j.jhazmat.2014.06.035.

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25

Eckert, Timothy, Grace Harmeyer, Steven Legate, and Steven Mathe. "A Rationale for the Ortho Effect in Electrophilic Aromatic Substitutions." Letters in Organic Chemistry 17, no. 9 (2020): 655–58. http://dx.doi.org/10.2174/1570178617666200207103755.

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The ortho effect arises in certain electrophilic aromatic substitutions when a meta director is meta to an ortho/para director. Among the three expected isomer products, only the two isomers ortho to the meta director are produced normally. To find an explanation for the ortho effect, nitrations of two properly substituted benzenes were explored. Evidence supported an explanation based on resonance involving the meta director.
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26

Bergbreiter, David E., Chris Hobbs, Jianhua Tian, Hisao Koizumi, Haw-Lih Su, and Chayanant Hongfa. "Synthesis of aryl-substituted polyisobutylenes as precursors for ligands for greener, phase-selectively soluble catalysts." Pure and Applied Chemistry 81, no. 11 (2009): 1981–90. http://dx.doi.org/10.1351/pac-con-08-10-09.

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General synthetic approaches to functional derivatives of polyisobutylene (PIB) that contain arene groups that can be used as catalysts or as precursors to catalyst ligands are discussed. The emphasis is on reactions that use commercially available terminally functionalized PIB derivatives as starting materials. Both successful and unsuccessful electrophilic aromatic substitution processes are described, and potential problems of this process and ways to circumvent the problem of depolymerization of the intermediate polyisobutyl cation in substitutions of less reactive arenes are detailed. Exa
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27

Lakhdar, Sami, and Herbert Mayr. "Counterion effects in iminium-activated electrophilic aromatic substitutions of pyrroles." Chem. Commun. 47, no. 6 (2011): 1866–68. http://dx.doi.org/10.1039/c0cc04295a.

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28

Schreiner, Peter R., Paul v. R. Schleyer, and Henry F. Schaefer. "Mechanisms of electrophilic substitutions of aliphatic hydrocarbons: methane + nitrosonium cation." Journal of the American Chemical Society 115, no. 21 (1993): 9659–66. http://dx.doi.org/10.1021/ja00074a035.

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29

Tomberg, Anna, Magnus J. Johansson, and Per-Ola Norrby. "A Predictive Tool for Electrophilic Aromatic Substitutions Using Machine Learning." Journal of Organic Chemistry 84, no. 8 (2018): 4695–703. http://dx.doi.org/10.1021/acs.joc.8b02270.

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30

KAPPE, T. "ChemInform Abstract: Nucleophilic and Electrophilic Substitutions at the Pyridazine Nucleus." ChemInform 26, no. 15 (2010): no. http://dx.doi.org/10.1002/chin.199515312.

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31

Brückner, Reinhard, and Rolf Huisgen. "Electrophilic substitutions by 2,2-bis(trifluoromethyl)ethylene-1,1-dicarbonitrile via addition." Tetrahedron Letters 32, no. 16 (1991): 1871–74. http://dx.doi.org/10.1016/s0040-4039(00)85984-5.

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32

DO, Q. T., D. ELOTHMANI, and G. LE GUILLANTON. "ChemInform Abstract: Electrophilic Substitutions with the Electrogenerated Sulfenium Cation R1-S+." ChemInform 29, no. 35 (2010): no. http://dx.doi.org/10.1002/chin.199835036.

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33

Mąkosza, Mieczysław. "Electrophilic and Nucleophilic Aromatic Substitutions are Mechanistically Similar with Opposite Polarity." Chemistry – A European Journal 26, no. 67 (2020): 15346–53. http://dx.doi.org/10.1002/chem.202003770.

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34

Kočovský, Pavel. "Organic Reactivity Control by Means of Neighboring Groups and Organometallics. A Personal Account." Collection of Czechoslovak Chemical Communications 59, no. 1 (1994): 1–74. http://dx.doi.org/10.1135/cccc19940001.

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This review summarizes the main topics of our research and covers the period of the last 15 years. The prime interest is focused on various ways of controlling the regio- and stereoselectivity of selected organic reactions, in particular electrophilic additions, cleavage of cyclopropane rings, and allylic substitutions by means of neighboring groups and/or transition and non-transition metals. In the first part, the factors governing the course of electrophilic additions are assessed, culminating in the formulation of selection rules for the reactivity of cyclohexene systems, and in a concise
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35

Ebine, Seiji, Kazuko Takahashi, and Tetsuo Nozoe. "Electrophilic and Nucleophilic Substitutions of 2-Amino- and 2-Hydroxy-1,3-diazaazulenes." Bulletin of the Chemical Society of Japan 61, no. 7 (1988): 2690–92. http://dx.doi.org/10.1246/bcsj.61.2690.

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36

Terrier, Fran�ois, Marie-Jos� Pouet, Jean-Claude Halle, Stephen Hunt, John R. Jones, and Erwin Buncel. "Electrophilic heteroaromatic substitutions: reactions of 5-X-substituted indoles with 4,6-dinitrobenzofuroxan." Journal of the Chemical Society, Perkin Transactions 2, no. 9 (1993): 1665. http://dx.doi.org/10.1039/p29930001665.

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37

Rao, K. Vara Prasad, and V. Sundaramurthy. "Regioselective electrophilic substitutions of 4H-imidazo[2,1-c][1,4]benzoxa(thia)zines." Journal of Organic Chemistry 57, no. 9 (1992): 2737–39. http://dx.doi.org/10.1021/jo00035a037.

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38

Enders, Dieter, Pascal Teschner, Gerhard Raabe та Jan Runsink. "Asymmetric Electrophilic Substitutions at the α-Position of γ- and δ-Lactams". European Journal of Organic Chemistry 2001, № 23 (2001): 4463–77. http://dx.doi.org/10.1002/1099-0690(200112)2001:23<4463::aid-ejoc4463>3.0.co;2-1.

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39

Aeyad, Tahani, Jason Williams, Anthony Meijer, and Iain Coldham. "Lithiation–Substitution of N-Boc-2-phenylazepane." Synlett 28, no. 20 (2017): 2765–68. http://dx.doi.org/10.1055/s-0036-1590857.

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Preparation of 2,2-disubstituted azepanes was accomplished from N-tert-butoxy(N-Boc)-2-phenylazepane by treatment with butyllithium then electrophilic quench. The lithiation was followed by in situ ReactIR spectroscopy and the rate of rotation of the carbamate was determined by variable temperature (VT)-NMR spectroscopy and by DFT studies. Most electrophiles add α to the nitrogen atom but cyanoformates and chloroformates gave ortho-substituted products. Cyclic carbamates were formed from an aldehyde or ketone electrophile. Kinetic resolution with sparteine was only poorly selective. Removal of
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40

Cecchi, Patrizio, Adriano Pizzabiocca, Gabriele Renzi, Cinzia Sparapani, and Maurizio Speranza. "Gas-phase heteroaromatic substitution. 14. Attack of dimethylfluoronium ion on 2- and 3-methyl-pyrroles, -furans, and -thiophenes." Canadian Journal of Chemistry 69, no. 12 (1991): 2094–103. http://dx.doi.org/10.1139/v91-302.

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The gas-phase methylation of 2- and 3-methyl-pyrroles (2P and 3P), -furans (2F and 3F), and -thiophenes (2T and 3T) by (CH3)2F+ ions, from γ radiolysis of CH3F, has been investigated at pressures ranging from 50 to 760 Torr, in the presence of a thermal radical scavenger (O2) and variable concentrations of an added base (NMe3: 0–10 Torr). The mechanism of the methylation process is discussed and the intrinsic positional selectivity of the (CH3)2F+ ions evaluated in the framework of the Charge and Frontier Orbital Control concept. Owing to the very large energy gap between the LUMO of (CH3)2F+
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41

Razus, Alexandru C. "Azulene, Reactivity, and Scientific Interest Inversely Proportional to Ring Size; Part 1: The Five-Membered Ring." Symmetry 15, no. 2 (2023): 310. http://dx.doi.org/10.3390/sym15020310.

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The lack of azulene symmetry with respect to the axis perpendicular to a molecule creates an asymmetry of the electronic system, increasing the charge density of the five-atom ring and favoring its electrophilic substitutions. The increased reactivity of this ring has contributed to ongoing interest about the syntheses in which it is involved. The aim of this review is to present briefly and mainly in the form of reaction schemes the behavior of this system. After a short chapter that includes the research until 1984, subsequent research is presented as generally accepted chapters and subchapt
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42

Salcedo, Roberto, Norma Mireles, and Luis Enrique Sansores. "Aromaticity in Substituted [2,2]Paracyclophane: A Density Functional Study." Journal of Theoretical and Computational Chemistry 02, no. 02 (2003): 171–77. http://dx.doi.org/10.1142/s0219633603000422.

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Inductive effect in the aromatic moieties of [2,2]paracyclophane is theoretically analyzed with the density functional theory. The inclusion of different substituents in one of the moieties seems to affect the behaviour of the other. The nature of activating or deactivating groups as substituents reflect known facts on electrophilic aromatic substitutions derived from the inductive effects. The interesting feature in this case is that the phenomenon is transfered from the substituted deck to the other via transannular effects. The strain suffered by the cyclophane molecule is also analyzed.
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43

Srinivas, Kolupula, Brice Kauffmann, Christel Dolain, Jean-Michel Léger, Léon Ghosez, and Ivan Huc. "Remote Substituent Effects and Regioselective Enhancement of Electrophilic Substitutions in Helical Aromatic Oligoamides." Journal of the American Chemical Society 130, no. 40 (2008): 13210–11. http://dx.doi.org/10.1021/ja805178j.

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44

Tseng, Hsing-Chang, Arun Kumar Gupta, Bor-Cherng Hong, and Ju-Hsiou Liao. "Regioselective electrophilic substitutions of fulvenes with ethyl glyoxylate and subsequent Diels–Alder reactions." Tetrahedron 62, no. 7 (2006): 1425–32. http://dx.doi.org/10.1016/j.tet.2005.11.029.

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45

BRUECKNER, R., and R. HUISGEN. "ChemInform Abstract: Electrophilic Substitutions by 2,2-Bis(trifluoromethyl)ethylene-1,1- dicarbonitrile via Addition." ChemInform 23, no. 4 (2010): no. http://dx.doi.org/10.1002/chin.199204062.

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46

Pindur, Ulf, and Camran Flo. "First Electrophilic Substitutions of 3-Substituted Indoles with Diethoxycarbenium Tetrafluoroborate: Functionalized Indole Derivatives." Archiv der Pharmazie 323, no. 2 (1990): 79–81. http://dx.doi.org/10.1002/ardp.19903230205.

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47

Abel, Silvestre Bongiovanni, Evelina Frontera, Diego Acevedo, and Cesar A. Barbero. "Functionalization of Conductive Polymers through Covalent Postmodification." Polymers 15, no. 1 (2022): 205. http://dx.doi.org/10.3390/polym15010205.

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Organic chemical reactions have been used to functionalize preformed conducting polymers (CPs). The extensive work performed on polyaniline (PANI), polypyrrole (PPy), and polythiophene (PT) is described together with the more limited work on other CPs. Two approaches have been taken for the functionalization: (i) direct reactions on the CP chains and (ii) reaction with substituted CPs bearing reactive groups (e.g., ester). Electrophilic aromatic substitution, SEAr, is directly made on the non-conductive (reduced form) of the CPs. In PANI and PPy, the N-H can be electrophilically substituted. T
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48

Atta, Kamal F. M. "Synthesis and Electrophilic Substitutions of Novel Pyrazolo[1,5-c]-1,2,4-triazolo[4,3-a]pyrimidines." Molecules 16, no. 8 (2011): 7081–96. http://dx.doi.org/10.3390/molecules16087081.

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49

Mongin, Florence, Antonio Tognini, Fabrice Cottet, and Manfred Schlosser. "Halogen shuffling in pyridines: Site selective electrophilic substitutions of 2-chloro-6-(trifluoromethyl)pyridine." Tetrahedron Letters 39, no. 13 (1998): 1749–52. http://dx.doi.org/10.1016/s0040-4039(98)00028-8.

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50

Herrlich, Mirjam, Nathalie Hampel, and Herbert Mayr. "Electrophilic Aromatic Substitutions of Silylated Furans and Thiophenes with Retention of the Organosilyl Group." Organic Letters 3, no. 11 (2001): 1629–32. http://dx.doi.org/10.1021/ol015810+.

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