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Synthesis 2011(17): 2709-2720  
DOI: 10.1055/s-0030-1260141
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© Georg Thieme Verlag Stuttgart ˙ New York

Lewis Acid or Alkyl Halide Promoted Rearrangements of Phosphor- and Phosphinimidates to N,N-Disubstituted Phosphor- and Phosphinamidates

Ina Wilkening, Giuseppe del Signore, Wiebke Ahlbrecht, Christian P. R. Hackenberger*
Freie Universität Berlin, Institut für Chemie und Biochemie, Takustr. 3, 14195 Berlin, Germany
Fax: +49(30)83852551; e-Mail: hackenbe@chemie.fu-berlin.de;
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Publication History

Received 4 May 2011
Publication Date:
27 July 2011 (online)

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Abstract

In this paper, we describe the synthesis of N,N-disubstituted phosphor- and phosphinamidates via alkyl halide or Lewis acid catalyzed rearrangements of phosphor- or phosphinimidates. Furthermore, we introduce a novel one-pot procedure for the synthesis of N,N-disubstituted phosphoramidates which prevents the isolation of potentially explosive alkyl azide derivatives. In this reaction sequence, several alkyl halides are converted in situ into the corresponding azides and reacted with phosphites to generate phosphorimidates. Final addition of a catalytic amount of Lewis acid to the mixture affords the N,N-disubstituted phosphoramidates in good to excellent overall yields.

1 Introduction

2 Synthesis of N,N-Disubstituted Phosphor- and Phosphinamidates

2.1 Alkyl Halide Catalyzed Rearrangement of Phosphin- and Phosphorimidates

2.2 Lewis Acid Catalyzed Rearrangement of Phosphin- and Phosphorimidates

2.3 One-Pot Procedure for the Formation of N,N-Disubstituted Phosphoramidates from Alkyl Halides

3 Conclusion

Key words

Staudinger reaction - phosphorimidate rearrangement - phosphoramidates - phosphinamidate - one-pot procedure - Lewis acid catalysis

    References

  • 1a Cheon CH. Yamamoto H. J. Am. Chem. Soc.  2008,  130:  9246 
    Search in Google Scholar
  • 1b Denmark SE. Stavenger RA. Wong KT. Su XP. J. Am. Chem. Soc.  1999,  121:  4982 
    Search in Google Scholar
  • 1c Enders D. Narine AA. Toulgoat F. Bisschops T. Angew. Chem. Int. Ed.  2008,  47:  5661 
    Search in Google Scholar
  • 1d Jiao P. Nakashima D. Yamamoto H. Angew. Chem. Int. Ed.  2008,  47:  2411 
    Search in Google Scholar
  • 1e Nakashima D. Yamamoto H. J. Am. Chem. Soc.  2006,  128:  9626 
    Search in Google Scholar
  • 1f Rueping M. Azap C. Angew. Chem. Int. Ed.  2006,  45:  7832 
    Search in Google Scholar
  • 1g Rueping M. Ieawsuwan W. Antonchick AP. Nachtsheim BJ. Angew. Chem. Int. Ed.  2007,  46:  2097 
    Search in Google Scholar
  • 1h Rueping M. Nachtsheim BJ. Moreth SA. Bolte M. Angew. Chem. Int. Ed.  2008,  47:  593 
    Search in Google Scholar
  • 1i Lee EE. Batey RA. J. Am. Chem. Soc.  2005,  127:  14887 
    Search in Google Scholar
  • 2a Wilkening I. del Signore G. Hackenberger CPR. Chem. Commun.  2011,  47:  349 
    Search in Google Scholar
  • 2b Bartlett PA. Marlowe CK. Biochemistry  1983,  22:  4618 
    Search in Google Scholar
  • 2c Jacobsen NE. Bartlett PA. J. Am. Chem. Soc.  1981,  103:  654 
    Search in Google Scholar
  • 2d Mookhtiar KA. Marlowe CK. Bartlett PA. Vanwart HE. Biochemistry  1987,  26:  1962 
    Search in Google Scholar
  • 2e Radkiewicz JL. McAllister MA. Goldstein E. Houk KN. J. Org. Chem.  1998,  63:  1419 
    Search in Google Scholar
  • 2f Grembecka J. Mucha A. Cierpicki T. Kafarski P. J. Med. Chem.  2003,  46:  2641 
    Search in Google Scholar
  • 2g Holden HM. Tronrud DE. Monzingo AF. Weaver LH. Matthews BW. Biochemistry  1987,  26:  8542 
    Search in Google Scholar
  • 2h Izquierdo-Martin M. Stein RL. J. Am. Chem. Soc.  1992,  114:  1527 
    Search in Google Scholar
  • 3a Adelfinskaya O. Herdewijn P. Angew. Chem. Int. Ed.  2007,  46:  4356 
    Search in Google Scholar
  • 3b Perrone P. Daverio F. Valente R. Rajyaguru S. Martin JA. Leveque V. Le Pogam S. Najera I. Klumpp K. Smith DB. McGuigan C. J. Med. Chem.  2007,  50:  5463 
    Search in Google Scholar
  • 3c Roman CA. Balzarini J. Meier C. J. Med. Chem.  2010,  53:  7675 
    Search in Google Scholar
  • 3d Siddiqui AQ. McGuigan C. Ballatore C. Zuccotto F. Gilbert IH. De Clercq E. Balzarini J. J. Med. Chem.  1999,  42:  4122 
    Search in Google Scholar
  • 3e Tobias SC. Borch RF. J. Med. Chem.  2001,  44:  4475 
    Search in Google Scholar
  • 4a Serwa R. Wilkening I. Del Signore G. Mühlberg M. Claussnitzer I. Weise C. Gerrits M. Hackenberger CPR. Angew. Chem. Int. Ed.  2009,  48:  8234 
    Search in Google Scholar
  • 4b Böhrsch V. Serwa R. Majkut P. Krause E. Hackenberger CPR. Chem. Commun.  2010,  46:  3176 
    Search in Google Scholar
  • 4c Serwa R. Majkut P. Horstmann B. Swiecicki JM. Gerrits M. Krause E. Hackenberger CPR. Chem. Sci.  2010,  1:  596 
    Search in Google Scholar
  • 4d Serwa R. Swiecicki J.-M. Homann D. Hackenberger CPR. J. Pept. Sci.  2010,  16:  563 
    Search in Google Scholar
  • 4e Jaradat DMM. Hamouda H. Hackenberger CPR. Eur. J. Org. Chem.  2010,  5004 
  • 5a Das S. Das U. Selvakumar P. Sharma RK. Balzarini J. De Clercq E. Molnar J. Serly J. Barath Z. Schatte G. Bandy B. Gorecki DKJ. Dimmock JR. ChemMedChem  2009,  4:  1831 
    Search in Google Scholar
  • 5b Ramage R. Hopton D. Parrott MJ. Richardson RS. Kenner GW. Moore GA. J. Chem. Soc., Perkin Trans. 1  1985,  461 
  • 6a Popovici C. Ona-Burgos P. Fernandez I. Roces L. Garcia-Granda S. Iglesias MJ. Ortiz FL. Org. Lett.  2010,  12:  428 
    Search in Google Scholar
  • 6b Ruiz-Gomez G. Iglesias MJ. Serrano-Ruiz M. Garcia-Granda S. Francesch A. Lopez-Ortiz F. Cuevas C. J. Org. Chem.  2007,  72:  3790 
    Search in Google Scholar
  • 7 Staudinger H. Helv. Chim. Acta  1919,  2:  635 
    CrossrefSearch in Google Scholar
  • 8a Gololobov YG. Kasukhin LF. Tetrahedron  1992,  48:  1353 
    Search in Google Scholar
  • 8b Gololobov YG. Zhmurova IN. Kasukhin LF. Tetrahedron  1981,  37:  437 
    Search in Google Scholar
  • 8c Gololobov YG. Kasukhin LF. Petrenko VS. Phosphorus, Sulfur Silicon Relat. Elem.  1987,  30:  393 
    Search in Google Scholar
  • 9 Kohn M. Breinbauer R. Angew. Chem. Int. Ed.  2004,  43:  3106 
    CrossrefPubMedSearch in Google Scholar
  • 10a Lin FL. Hoyt HM. van Halbeek H. Bergman RG. Bertozzi CR. J. Am. Chem. Soc.  2005,  127:  2686 
    Search in Google Scholar
  • 10b Saxon E. Bertozzi CR. Science  2000,  287:  2007 
    Search in Google Scholar
  • 10c Saxon E. Luchansky SJ. Hang HC. Yu C. Lee SC. Bertozzi CR. J. Am. Chem. Soc.  2002,  124:  14893 
    Search in Google Scholar
  • 11 Wilkening I. del Signore G. Hackenberger CPR. Chem. Commun.  2008,  2932 
  • 12 Challis BC. Challis JA. Iley JN. J. Chem. Soc., Perkin Trans. 2  1978,  813 
  • 13 Chen B. Mapp AK. J. Am. Chem. Soc.  2004,  126:  5364 
    CrossrefSearch in Google Scholar
  • 14 Challis BC. Frenkel AD. J. Chem. Soc., Perkin Trans. 2  1978,  192 
  • 15a Gilyarov VA. Kvasov BA. Shcherbina TM. Kabachnik MI. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.)  1980,  29:  136 
    Search in Google Scholar
  • 15b Shcherbina TM. Laretina AP. Gilyarov VA. Kabachnik MI. Russ. Chem. Bull.  1994,  43:  641 
    Search in Google Scholar
  • 15c Gilyarov VA. Shcherbina TM. Laretina AP. Kabachnik MI. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.)  1992,  41:  1931 
    Search in Google Scholar
  • 15d Shcherbina TM. Laretina AP. Gilyarov VA. Korkin AA. Kabachnik MI. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.)  1991,  40:  239 
    Search in Google Scholar
  • 16 Challis BC. Frenkel AD. J. Chem. Soc., Chem. Commun.  1972,  303 
  • 17 Shintou T. Kikuchi W. Mukaiyama T. Bull. Chem. Soc. Jpn.  2003,  76:  1645 
    CrossrefSearch in Google Scholar
  • 18 Bräse S. Gil C. Knepper K. Zimmermann V. Angew. Chem. Int. Ed.  2005,  44:  5188 
    CrossrefPubMedSearch in Google Scholar
  • 19 Gefflaut T. Lemaire M. Valentin M.-L. Bolte J. J. Org. Chem.  1997,  62:  5920 
    CrossrefSearch in Google Scholar
  • 20 Bigg DCH. Spratt RB. Walker J. Tetrahedron Lett.  1970,  1:  107 
    Search in Google Scholar