Anhydrous Phosphazenium Fluorides as Sources for Extremely Reactive Fluoride Ions in Solution
Abstract
Several peralkylated polyaminophosphazenium cations were evaluated for the generation of novel anhydrous F− salts. Two of them have been characterized by X‐ray analysis and are particularly soluble, even in apolar aprotic solvents like benzene or THF, one of them even at −30 °C. Such solutions probably represent the most basic metal‐free and stable media known to date. Comparison of these fluorides with known F− sources demonstrates that they are of unprecedented reactivity and selectivity in E2 elimination reactions.
Number of times cited: 33
- Kevin D. Dykstra, Naoko Ichiishi, Shane W. Krska and Paul F. Richardson, Emerging fluorination methods in organic chemistry relevant for life science application, Fluorine in Life Sciences: Pharmaceuticals, Medicinal Diagnostics, and Agrochemicals, 10.1016/B978-0-12-812733-9.00001-5, (1-90), (2019).
- Sandip S. Shinde, Nilesh S. Khonde and Pradeep Kumar, Tri–tert‐Butanolamine as an Organic Promoter in Nucleophilic Fluorination, ChemistrySelect, 2, 1, (118-122), (2017).
- Shengzong Liang, Gerald B. Hammond and Bo Xu, Hydrogen Bonding: Regulator for Nucleophilic Fluorination, Chemistry – A European Journal, 23, 71, (17850-17861), (2017).
- C. Tyler Womble, Jamie Kang, Kristina M. Hugar, Geoffrey W. Coates, Stefan Bernhard and Kevin J. T. Noonan, Rapid Analysis of Tetrakis(dialkylamino)phosphonium Stability in Alkaline Media, Organometallics, 10.1021/acs.organomet.7b00663, 36, 20, (4038-4046), (2017).
- Shlomi Elias, Naama Karton-Lifshin, Lea Yehezkel, Nissan Ashkenazi, Ishay Columbus and Yossi Zafrani, Synthesis, Characterization, and Reactivity of Thermally Stable Anhydrous Quaternary Ammonium Fluorides, Organic Letters, 19, 12, (3039), (2017).
- Liyan Wang, Xiaohuan Jiang and Pingping Tang, Silver-mediated fluorination of alkyl iodides with TMSCF 3 as the fluorinating agent , Organic Chemistry Frontiers, 10.1039/C7QO00450H, 4, 10, (1958-1961), (2017).
- Ji-Woong Lee, Maria Teresa Oliveira, Hyeong Bin Jang, Sungyul Lee, Dae Yoon Chi, Dong Wook Kim and Choong Eui Song, Hydrogen-bond promoted nucleophilic fluorination: concept, mechanism and applications in positron emission tomography, Chem. Soc. Rev., 10.1039/C6CS00286B, 45, 17, (4638-4650), (2016).
- Damien Jardel, Clotilde Davies, Frédéric Peruch, Stéphane Massip and Brigitte Bibal, Protonated Phosphazenes: Structures and Hydrogen‐Bonding Organocatalysts for Carbonyl Bond Activation, Advanced Synthesis & Catalysis, 358, 7, (1110-1118), (2016).
- Hans J. Reich, Mechanism of C–Si Bond Cleavage Using Lewis Bases (n → σ*), Lewis Base Catalysis in Organic Synthesis, (233-280), (2016).
- Michael G. Campbell and Tobias Ritter, Modern Carbon–Fluorine Bond Forming Reactions for Aryl Fluoride Synthesis, Chemical Reviews, 10.1021/cr500366b, 115, 2, (612-633), (2014).
- Yuki Takada, Siong Wan Foo, Yusuke Yamazaki and Susumu Saito, Catalytic fluoride triggers dehydrative oxazolidinone synthesis from CO 2 , RSC Adv., 10.1039/C4RA09609F, 4, 92, (50851-50857), (2014).
- Christoph Bolli, Jorit Gellhaar, Carsten Jenne, Mathias Keßler, Harald Scherer, Helene Seeger and Rabiya Uzun, Bis(triphenyl-λ5-phosphanylidene)ammonium fluoride: a reactive fluoride source to access the hypervalent silicates [MenSiF5−n]−(n = 0–3), Dalton Trans., 43, 11, (4326), (2014).
- Kiyofumi Inamoto, Hitomi Okawa, Shoko Kikkawa and Yoshinori Kondo, Use of tetramethylammonium fluoride (TMAF) and alkali metal alkoxides as an activator for catalytic deprotonative functionalization of heteroaromatic C(sp2)–H bonds, Tetrahedron, 10.1016/j.tet.2014.08.054, 70, 43, (7917-7922), (2014).
- Fátima García, Juan Aragó, Rafael Viruela, Enrique Ortí and Luis Sánchez, A bis(triazole)benzamide receptor for the complexation of halide anions and neutral carboxylic acid guests. Guest-controlled topicity and self-assembly, Org. Biomol. Chem., 10.1039/C2OB26797G, 11, 5, (765-772), (2013).
- Vincent Diemer, Juan Sanz Garcia, Frédéric R. Leroux and Françoise Colobert, Aryne-mediated fluorination: Synthesis of fluorinated biaryls via a sequential desilylation–halide elimination–fluoride addition process, Journal of Fluorine Chemistry, 10.1016/j.jfluchem.2011.02.017, 134, (146-155), (2012).
- Josefredo R. Pliego and Jose M. Riveros, New insights on reaction pathway selectivity promoted by crown ether phase-transfer catalysis: Model ab initio calculations of nucleophilic fluorination, Journal of Molecular Catalysis A: Chemical, 10.1016/j.molcata.2012.07.030, 363-364, (489-494), (2012).
- Kiyofumi Inamoto, Hitomi Okawa, Hiroshi Taneda, Maomi Sato, Yutaro Hirono, Misato Yonemoto, Shoko Kikkawa and Yoshinori Kondo, Organocatalytic deprotonative functionalization of C(sp2)–H and C(sp3)–H bonds using in situ generated onium amide bases, Chemical Communications, 48, 78, (9771), (2012).
- Bente Mathiessen, Andreas T. I. Jensen and Fedor Zhuravlev, Homogeneous Nucleophilic Radiofluorination and Fluorination with Phosphazene Hydrofluorides, Chemistry – A European Journal, 17, 28, (7796-7805), (2011).
- Josefredo R. Pliego Jr., Chemical reactions inside structured nano-environment: SN2vs. E2 reactions for the F−+ CH3CH2Cl system, Phys. Chem. Chem. Phys., 13, 2, (779), (2011).
- Dhilon S. Patel and Prasad V. Bharatam, Divalent N(I) Compounds with Two Lone Pairs on Nitrogen, The Journal of Physical Chemistry A, 115, 26, (7645), (2011).
- Daisuke Uraguchi, Yoshihiro Asai and Takashi Ooi, Site‐Directed Asymmetric Quaternization of a Peptide Backbone at a C‐Terminal Azlactone, Angewandte Chemie, 121, 4, (747-751), (2008).
- Mahesh K. Lakshman, Asad Choudhury, Suyeal Bae, Eliezer Rochttis, Padmanava Pradhan and Amit Kumar, Synthesis of N6,N6‐Dialkyladenine Nucleosides Using Hexaalkylphosphorus Triamides Produced in Situ , European Journal of Organic Chemistry, 2009, 1, (152-159), (2008).
- Indrajit Bandyopadhyay, Krishnan Raghavachari and Amar H. Flood, Strong CH⋅⋅⋅Halide Hydrogen Bonds from 1,2,3‐Triazoles Quantified Using Pre‐Organized and Shape‐Persistent Triazolophanes, ChemPhysChem, 10, 14, (2535-2540), (2009).
- Daisuke Uraguchi, Yoshihiro Asai and Takashi Ooi, Site‐Directed Asymmetric Quaternization of a Peptide Backbone at a C‐Terminal Azlactone, Angewandte Chemie International Edition, 48, 4, (733-737), (2008).
- Edgars Abele and Ramona Abele, Recent Advances in Activation of Silicon Bonds by Fluoride Ion, Main Group Metal Chemistry, 10.1515/MGMC.2009.32.4.165, 32, 4, (2009).
- Yu Liu, Zhe Li and Dong-Sheng Guo, Conformational transition effects of anion recognition by calix[4]arene derivatives, Supramolecular Chemistry, 10.1080/10610270802283085, 21, 6, (465-472), (2009).
- Roman A. Kunetskiy, Ivana Císařová, David Šaman and Ilya M. Lyapkalo, New Lipophilic 2‐Amino‐N,N′‐dialkyl‐4,5‐dimethylimidazolium Cations: Synthesis, Structure, Properties, and Outstanding Thermal Stability in Alkaline Media, Chemistry – A European Journal, 15, 37, (9477-9485), (2009).
- Josefredo R. Pliego, Jr and Dorila Piló-Veloso, Effects of ion-pairing and hydration on the SNAr reaction of the F − with p-chlorobenzonitrile in aprotic solvents , Phys. Chem. Chem. Phys., 10.1039/B716159J, 10, 8, (1118-1124), (2008).
- Vinod D. Jadhav, Eberhardt Herdtweck and Franz P. Schmidtchen, Addressing Association Entropy by Reconstructing Guanidinium Anchor Groups for Anion Binding: Design, Synthesis, and Host–Guest Binding Studies in Polar and Protic Solutions, Chemistry – A European Journal, 14, 20, (6098-6107), (2008).
- Thomas Mathew, Joern Tonne, Gottfried Sedelmeier, Clemens Grund, Manfred Keller, Dieter Hunkler, Lothar Knothe and Horst Prinzbach, [6+6]Photocycloadditions in Face‐to‐Face Benzo/Pyridazino Substrates – En Route to Azapagodanes , European Journal of Organic Chemistry, 2007, 13, (2133-2146), (2007).
- Axel Pleschke, Jens Geier, Manfred Keller, Jürgen Wörth, Lothar Knothe and Horst Prinzbach, In Pursuit of cis,cis,cis‐Cyclonona‐2,5,8‐triene‐1,4,7‐trione – An Adventure in Medium‐Sized Ring Chemistry, European Journal of Organic Chemistry, 2007, 29, (4867-4880), (2007).
- Martin Valik, Vladimir Král, Eberhardt Herdtweck and Franz P. Schmidtchen, Sulfoniumcalixpyrrole: the decoration of a calix[4]pyrrole host with positive charges boosts affinity and selectivity of anion binding in DMSO solvent, New J. Chem., 10.1039/B617465E, 31, 5, (703-710), (2007).
- Emmerich Sackers, Thomas Oßwald, Klaus Weber, Manfred Keller, Dieter Hunkler, Jürgen Wörth, Lothar Knothe and Horst Prinzbach, Bromination of Unsaturated Dodecahedranes—En Route to C20 Fullerene, Chemistry – A European Journal, 12, 24, (6242-6254), (2006).




