Download PDF
Synthesis 2012(1): 93-98  
DOI: 10.1055/s-0031-1289626
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Selective Protection and Deprotection of ortho-Functionalized Arylphosphonates

Elodie Lagadic, Yann Garcia, Jacqueline Marchand-Brynaert*
Université catholique de Louvain, Institute of Condensed Matter and Nanosciences (IMCN)- Molecules, Solids and Reactivity (MOST), Bâtiment Lavoisier, place Louis Pasteur, L4.01.02, 1348 Louvain-la-Neuve, Belgium
Fax: +32(10)474168; e-Mail: Jacqueline.Marchand@uclouvain.be;
Further Information

Publication History

Received 4 October 2011
Publication Date:
02 December 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

Functionalized aromatic alkylphosphonates, hemi-phosphonates and phosphonic acids are good candidates to elaborate water-soluble building blocks. The key step of the synthesis developed here consisted of the introduction of a phosphoryl group by an ortho-metallation reaction from protected ortho-anisidine. A practical route to phosphonated benzoxazoles was thus discovered. Chemoselective deprotections were investigated and mono-, bis-, and ter-deprotected aromatic derivatives were obtained.

Key words

chemoselectivity - cleavage - heterocycles - deprotection - aromatic phosphonates

    References

  • 1a Terada M. Synthesis  2010,  1929 
    Google Scholar
  • 1b Kerns EH. Di L. Drug-Like Properties: Concepts, Structure Design and Methods: from ADME to Toxicity Optimization   Elsevier/Academic Press; London: 2008. 
    Google Scholar
  • 1c Conway SJ. Miller JC. Howson PA. Clark BP. Jane DE. Bioorg. Med. Chem. Lett.  2001,  11:  777 
    Google Scholar
  • 2 Bruyneel F. D’Auria L. Payen O. Courtoy PJ. Marchand-Brynaert J. ChemBioChem  2010,  11:  1451 
    Google Scholar
  • 3 Latham K. White KF. Szpakolski KB. Rix CJ. White JM. Inorg. Chim. Acta  2009,  362:  1872 
    Google Scholar
  • 4 Kukhar V. Hudson H. Aminophosphonic and Aminophosphinic Acids: Chemistry and Biological Activity   John Wiley &αµπ; Sons; New York: 2000. 
    Google Scholar
  • 5 Defacqz N. De Bueger B. Touillaux R. Cordi A. Marchand-Brynaert J. Synthesis  1999,  1368 ; and references cited therein
    Google Scholar
  • 6a Bruyneel F. Enaud E. Billottet L. Vanhulle S. Marchand-Brynaert J. Eur. J. Org. Chem.  2008,  72 
    Google Scholar
  • 6b Bruyneel F. Payen O. Rescigno A. Tinant B. Marchand-Brynaert J. Chem. Eur. J.  2009,  15:  8283 
    Google Scholar
  • 6c Rescigno A. Bruyneel F. Padiglia A. Sollai F. Salis A. Marchand-Brynaert J. Sanjust E. Biochim. Biophys. Acta, Gen. Subj.  2011,  1810:  799 
    Google Scholar
  • 7a Robiette R. Defacqz N. Peeters D. Marchand-Brynaert J. Curr. Org. Synth.  2005,  2:  453 
    Google Scholar
  • 7b Beck J. Gharbi S. Herteg-Fernea A. Vercheval L. Bebrome C. Lassaux P. Zervosen A. Marchand-Brynaert J. Eur. J. Org. Chem.  2009,  85 
    Google Scholar
  • 7c Monbaliu J.-C. Marchand-Brynaert J. Synthesis  2009,  1876 
    Google Scholar
  • 7d Monbaliu J.-C. Villemin E. Elias B. Marchand-Brynaert J. Targets in Heterocyclic Systems   Vol. 14:  Attanasi OA. Spinelli D. Italian Society of Chemistry; Rome: 2010.  p.49-79  
    Google Scholar
  • 8a Maillet C. Praveen T. Janvier P. Minguet S. Evain M. Saluzzo C. Tommasino ML. Bujoli B. J. Org. Chem.  2002,  67:  8191 
    Google Scholar
  • 8b Mauger C. Masson S. Vazeux M. Saint-Clair J.-F. Midura WH. Drabowicz J. Mikolajczyk M. Tetrahedron: Asymmetry  2001,  12:  167 
    Google Scholar
  • 9 Morita T. Okamoto Y. Sakurai H. Tetrahedron Lett.  1978,  2523 
    Google Scholar
  • 10 Gauvry N. Mortier J. Synthesis  2001,  553 
    Google Scholar
  • 11 Smith AB. Ducry L. Corbett RM. Hirschmann R. Org. Lett.  2000,  2:  3887 
    Google Scholar
  • 12a Bruyneel F. Marchand-Brynaert J. Synlett  2010,  1974 
    Google Scholar
  • 12b Lavergne O. Fernandes A.-C. Bréhu L. Sidhu A. Brézak M.-C. Prévost G. Ducommun B. Contour-Galvera M.-O. Bioorg. Med. Chem. Lett.  2006,  16:  171 
    Google Scholar
  • 12c Nagamitsu T. Sunazuka T. Tanaka H. Omura S. Sprengeler PA. Smith AB. J. Am. Chem. Soc.  1996,  118:  3584 
    Google Scholar
  • 13 Yan F. Moon S.-J. Liu P. Zhao Z. Lipscomb JD. Liu A. Liu H.-W. Biochemistry  2007,  46:  12628 
    Google Scholar
  • 14 Garcia Y. Van Koningsbruggen PJ. Lapouyade R. Fournès L. Rabardel L. Kahn O. Ksenofontov V. Levchenko G. Gütlich P. Chem. Mater.  1998,  10:  2426 
    Google Scholar