Chemistry of Heterocyclic Compounds

, Volume 52, Issue 8, pp 541–545 | Cite as

Synthesis of Chiral Phosphazene Bases

  • Martins Priede
  • Elina Priede
  • Jaan Saame
  • Ivo Leito
  • Edgars Suna
Article

Air-stable and crystalline tetraaminophosphonium tetrafluoroborates possessing chiral, enantiomerically pure 1,2-diamine moiety have been synthesized by a three-step sequential one-pot approach. The tetrafluoroborate salts can be purified by recrystallization or chromatography and subsequently converted to the phosphazene bases by treatment with t-BuOK. Basicity values in tetrahydrofuran have been measured for the obtained phosphazene bases by means of spectrophotometric titration.

Keywords

phosphazene bases tetraaminophosphonium salts basicity one-pot synthesis pKip value 

Supplementary material

10593_2016_1927_MOESM1_ESM.pdf (325 kb)
ESM 1(PDF 325 kb)

References

  1. 1.
    (a) Herzberger, J.; Niederer, K.; Pohlit, H.; Seiwert, J.; Worm, M.; Wurm, F. R.; Frey, H. Chem. Rev. 2016, 116, 2170. (b) Kondo, Y. In Superbases for Organic Synthesis; Shikawa, T., Ed.; Wiley: Chichester, 2009, ch. 5. (c) Boileau, S.; Illy, N. Prog. Polym. Sci. 2011, 36, 1132. (d) Solladié-Cavallo, A.; Roje, M.; Welter, R.; Šunjić, V. J. Org. Chem. 2004, 69, 1409.Google Scholar
  2. 2.
    (a) Lee, Y.-J.; Lee, J.; Kim, M.-J.; Jeong, B.-S.; Lee, J.-H.; Kim, T.-S.; Lee, J.; Ku, J.-M.; Jew, S.-S.; Park, H.-G. Org. Lett. 2005, 7, 3207. (b) Solladié-Cavallo, A.; Crescenzi, B. Synlett 2000, 327.Google Scholar
  3. 3.
    (a) Brunel, J. M.; Legrand, O.; Reymond, S.; Buono, G. J. Am. Chem. Soc. 1999, 121, 5807. (b) Takeda, T.; Terada, M. J. Am. Chem. Soc. 2013, 135, 15306. (c) Uraguchi, D.; Ito, T.; Ooi, T. J. Am. Chem. Soc. 2009, 131, 3836. (d) Uraguchi, D.; Yoshioka, K.; Ueki, Y.; Ooi, T. J. Am. Chem. Soc. 2012, 134, 19370. (e) Uraguchi, D.; Tsutsumi, R.; Ooi, T. J. Am. Chem. Soc. 2013, 135, 8161.Google Scholar
  4. 4.
    (a) Schwesinger, R.; Schlemper, H.; Hasenfratz, C.; Willaredt, J.; Dambacher, T.; Breuer, T.; Ottaway, C.; Fletschinger, M.; Boele, J.; Fritz, H.; Putzas, D.; Rotter, H. W.; Bordwell, F. G.; Satish, A. V.; Ji, G.-Z.; Peters, E.-M.; Peters, K.; von Schnering, H. G.; Walz, L. Liebigs Ann. 1996, 1055. (b) Köhn, U.; Schulz, M.; Schramm, A.; Günther, W.; Görls, H.; Schenk, S.; Anders, E. Eur. J. Org. Chem. 2006, 4128. (c) Alexandrova, A. V.; Masek, T.; Polyakova, S. M.; Cisarova, I.; Saame, J.; Leito, I.; Lyapkalo, I. M. Eur. J. Org. Chem. 2013, 9, 1811.Google Scholar
  5. 5.
    (a) Alajarín, M.; López-Leonardo, C.; Berná, J. Tetrahedron 2006, 62, 6190. (b) Terada, M.; Goto, K.; Oishi, M.; Takeda, T.; Kwon, E.; Kondoh, A. Synlett 2013, 24, 2531. (c) Kögel, J. F.; Kneusels, N.-J.; Sundermeyer, J. Chem. Commun. 2014, 50, 4319.Google Scholar
  6. 6.
    (a) Vedejs, E.; Donde, Y. J. Org. Chem. 2000, 65, 2337. (b) Nettekoven, U.; Widhalm, M.; Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Mereiter, K.; Lutz, M.; Spek, A. L. Organometallics 2000, 19, 2299. (c) Colby, E. A.; Jamison,T. F. J. Org. Chem. 2003, 68, 156.Google Scholar
  7. 7.
    Tolman, C. A. Chem. Rev. 1977, 77, 313.CrossRefGoogle Scholar
  8. 8.
    (a) Kaljurand, I.; Rodima, T.; Leito, I.; Koppel, I. A.; Schwesinger, R. J. Org. Chem. 2000, 65, 6202. (b) Rodima, T.; Kaljurand, I.; Pihl, A.; Mäemets, V.; Leito, I.; Koppel, I. A. J. Org. Chem. 2002, 67, 1873. (c) Kaljurand, I.; Kütt, A.; Sooväli, L.; Rodima, T.; Mäemets, V.; Leito, I.; Koppel, I. A. J. Org. Chem. 2005, 70, 1019. (d) Kaljurand, I.; Rodima, T.; Pihl, A.; Mäemets, V.; Leito, I.; Koppel, I. A.; Mishima, M. J. Org. Chem. 2003, 68, 9988. (e) Kaljurand, I.; Saame, J.; Rodima, T.; Koppel, I.; Koppel, I. A.; Kögel, J. F.; Sundermeyer, J.; Köhn, U.; Coles, M. P.; Leito, I. J. Phys. Chem. A 2016, 120, 2591.Google Scholar
  9. 9.
    Alexakis, A.; Mutti, S.; Mangeney, P. J. Org. Chem. 1992, 57, 1224.CrossRefGoogle Scholar
  10. 10.
    Alexakis, A.; Aujard, I.; Kanger, T.; Mangeney, P. Org. Synth. 2004, 10, 312; 1999, 76, 23.Google Scholar
  11. 11.
    Mark, V. Org. Synth. 1966, 46, 42; 1973, 5, 602.Google Scholar
  12. 12.
    Bottaro, J. C.; Penwell, P. E.; Schmitt, R. J. Synth. Commun. 1997, 27, 1465.CrossRefGoogle Scholar
  13. 13.
    Andersen, J.; Madsen, U.; Björkling, F.; Liang, X. Synlett 2005, 2209.Google Scholar
  14. 14.
    G. M. Sheldrick, SHELXL-97: Program for the Solution of Crystal Structures. University of Gőttingen (1997).Google Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Martins Priede
    • 1
  • Elina Priede
    • 1
  • Jaan Saame
    • 2
  • Ivo Leito
    • 2
  • Edgars Suna
    • 1
  1. 1.Latvian Institute of Organic SynthesisRigaLatvia
  2. 2.Institute of ChemistryUniversity of TartuTartuEstonia

Personalised recommendations