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Synthesis 2009(21): 3579-3588  
DOI: 10.1055/s-0029-1216982
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Propargyl-Substituted Phosphonocarboxylates: Efficient Synthesis and Application to Click Chemistry

Oleg I Artyushina, Sergey N. Osipova, Gerd-Volker Röschenthalerb, Irina L. Odinets*a
a A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova str., 119991 Moscow, Russian Federation
Fax: +7(499)1355085; e-Mail: odinets@ineos.ac.ru;
b Institute of Inorganic & Physical Chemistry, University of Bremen, Leobener Str., 28334 Bremen, Germany
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Publication History

Received 6 March 2009
Publication Date:
28 August 2009 (online)

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Abstract

An efficient pathway for the selective preparation of monopropargyl-substituted phosphonocarboxylate (PC) has been developed via the addition of sodium acetylenide to ethylidenephosphonate. The reaction works perfectly on multi-gram scales. The synthesis of the corresponding methyl(propargyl)-, trifluoro­methyl(propargyl)-, and dipropargyl-substituted derivatives was elaborated based on direct alkylation of either the correspondingly substituted phosphonocarboxylates or methylene phosphonocarboxylate with excess of propargyl bromide. A series of novel potentially biologically active 1,2,3-triazole-containing phosphono­-carboxylates were synthesized using copper(I)-catalysed 1,3-dipolar cycloaddition of organic azides with propargyl-substituted phosphonocarboxylates.

Key words

phosphonocarboxylates - ethylidenephosphonate - alkylation - sodium acetylenide - 1,3-dipolar cycloaddition - azides - phosphorylated 1,2,3-triazoles

    References

  • 1a Breuer E. The development of bisphosphonates as drugs, In Analogue-based Drug Discovery   Fischer J. Ganellin CR. Wiley-VCH; Berlin: 2006.  p.371-384  
  • 1b Catterall JB. Cawston TE. Arthritis Research and Therapy  2002,  5:  12 
    Search in Google Scholar
  • 1c Graham R. Russell G. Pediatrics  2007,  119:  S150 
    Search in Google Scholar
  • 2a Fleisch H. Bisphosphonates in Bone Disease, In From the Laboratory to the Patient   Parthenon; New York: 1995. 
  • 2b Papapoulos SE. Landman JO. Bijvoet OLM. Loewik CWGM. Valkema R. Pauwels EKJ. Vermeij P. Bone  1992,  13:  S41 
    Search in Google Scholar
  • 2c Yates AJ. Rodan GA. Drug Discovery Today  1998,  3:  69 
    Search in Google Scholar
  • 2d Socrates E. Papapoulos MD. Am. J. Med.  1993,  95:  48S 
    Search in Google Scholar
  • 2e Giannini S. D’Angelo AL. Sartory GL. Passeri G. Garbonare LD. Crebaldi C. Obst. Gynecol.  1996,  88:  431 
    Search in Google Scholar
  • 2f Uludag H. Curr. Pharm. Des.  2002,  8:  99 
    Search in Google Scholar
  • 3a Szajnman SH. Montalvetti A. Wang Y. Docampo R. Rodriguez JB. Bioorg. Med. Chem. Lett.  2003,  13:  3231 
    Search in Google Scholar
  • 3b Garzoni LR. Caldera A. Nazareth L. Meirelles M. Castro SL. Docampo R. Meints GA. Oldfield E. Urbina JA. Int. J. Antimicrob. Agents  2004,  23:  273 
    Search in Google Scholar
  • 3c Garzoni LR. Waghabi MC. Baptista MM. Castro SL. Nazareth L. Meirelles M. Britto CC. Docampo R. Oldfield E. Urbina JA. Int. J. Antimicrob. Agents  2004,  23:  286 
    Search in Google Scholar
  • 3d Kotsikorou E. Song Y. Chan JMW. Faelens S. Tovian Z. Broderick E. Bakalara N. Docampo R. Oldfield E. J. Med. Chem.  2005,  48:  6128 
    Search in Google Scholar
  • 4a Sanders JM. Song Y. Chan JMW. Zhang Y. Jennings S. Kosztowski T. Odeh S. Flessner R. Schwerdtfeger C. Kotsikorou E. Meints GA. Gomez AO. Gonzalez-Pacanowska D. Raker AM. Wang H. van Beek ER. Papapoulos SE. Morita CT. Oldfield E. J. Med. Chem.  2005,  48:  2957 
    Search in Google Scholar
  • 4b Coxon FP. Ebetino FH. Mules EH. Seabra MC. McKenna CE. Rogers MJ. Bone  2005,  37:  349 
    Search in Google Scholar
  • 5a Rogers MJ. Curr. Pharm. Des.  2003,  9:  2643 
    Search in Google Scholar
  • 5b Sato M. Grasser W. Endo N. Akins R. Simmons H. Thompson DD. Golub E. Rodan GA. J. Clin. Invest.  1991,  88:  2095 
    Search in Google Scholar
  • 5c Masarachia P. Weinreb M. Balena R. Rodan GA. Bone  1996,  19:  281 
    Search in Google Scholar
  • 5d Dunford JE. Thompson K. Coxon FP. Luckman SP. Hahn FM. Poulter CD. Ebetino FH. Rogers MJ. J. Pharmacol. Exp. Ther.  2001,  296:  235 
    Search in Google Scholar
  • 6a van Beek ER. Lowik C. van der Pluijm G. Papalous SE. J. Bone Miner. Res.  1999,  14:  722 
    Search in Google Scholar
  • 6b Coxon FP. Helfrich MH. Van’t HofR. Sebti S. Ralston SH. Hamilton AD. Rogers MJ. J. Bone Miner. Res.  2000,  15:  1467 
    Search in Google Scholar
  • 6c Graham R. Russell G. Pediatrics  2007,  119:  S150 
    Search in Google Scholar
  • 7 Engel R. Handbook of Organophosphorus Chemistry   Marcel Dekker; New York: 1992.  Chap. 11.
  • 8a Grem JL. King SA. O’Dwyer PJ. Leyland-Jones B. Cancer Res.  1988,  48:  4441 
    Search in Google Scholar
  • 8b Allewell NM. Shi D. Morizono H. Tuchman M. Acc. Chem. Res.  1999,  32:  885 
    Search in Google Scholar
  • 8c Fetler L. Tauc P. Hervé G. Cunin R. Brochon J.-C. Biochemistry  2001,  40:  8773 
    Search in Google Scholar
  • 8d Christopherson RI. Lyons SD. Wilson PK. Acc. Chem. Res.  2002,  35:  961 
    Search in Google Scholar
  • 9 Skarpos H. Osipov SN. Vorob’eva DV. Odinets IL. Lork E. Röschenthaler G.-V. J. Org. Biomol. Chem.  2007,  5:  2361 
    CrossrefSearch in Google Scholar
  • 10a Meldal M. Tornøe CW. Chem. Rev.  2008,  108:  2952 
    Search in Google Scholar
  • 10b Tron GC. Pirali T. Billington RA. Canonico PL. Sorba G. Genazzani AA. Med. Res. Rev.  2008,  28:  278 ; and references cited therein
    Search in Google Scholar
  • 11 Artyushin OI. Vorob’eva DV. Vasil’eva TP. Osipov SN. Roeschenthaler G.-V. Odinets IL. Heteroat. Chem.  2008,  19:  293 
    CrossrefSearch in Google Scholar
  • 12 Chang K.-H. Lee L. Chen J. Li W.-S. Chem. Commun.  2006,  629 
    Crossref
  • 13 Kirschleger B. Quengnec R. Synthesis  1986,  926 
    Thieme Connect
  • 14 Chambers JR. Isbell AF. J. Org. Chem.  1964,  29:  832 
    CrossrefSearch in Google Scholar
  • 15 Ravikumar VT. Swaminathan S. Rajagopalan K. Tetrahedron Lett.  1984,  6045 
    Crossref
  • 16 Blaszczyk E. Krawczyk H. Janecki T. Synlett  2004,  2685 
    Thieme Connect
  • 17 Pudovik AN. Khusainova NG. Zh. Obshch. Khim.  1969,  39:  2426 
    Search in Google Scholar
  • 18a Lee LV. Mitchell L. Huang S.-J. Fokin VV. Sharpless KB. Wong C.-H. J. Am. Chem. Soc.  2003,  125:  9588 
    Search in Google Scholar
  • 18b Appukkuttan P. Dehaen W. Fokin VV. van der Eycken E. Org. Lett.  2004,  6:  4223 
    Search in Google Scholar
  • 18c Feldman AK. Colasson B. Fokin VV. Org. Lett.  2004,  6:  3897 
    Search in Google Scholar
  • 19 Machleidt H. Wessendort R. Justus Liebigs Ann. Chem.  1964,  674:  1 
    CrossrefSearch in Google Scholar
  • 20a Dolby LJ. Riddle GN. J. Org. Chem.  1967,  32:  3481 
    Search in Google Scholar
  • 20b Gallagher G. Webb RL. Synthesis  1974,  122