Download PDF
Synthesis 2011(16): 2651-2663  
DOI: 10.1055/s-0030-1260110
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Direct Access to 3-Aminoindazoles by Buchwald-Hartwig C-N Coupling Reaction

Elodie Lohou, Valérie Collot*, Silvia Stiebing, Sylvain Rault
CERMN UPRES EA-4258, FR CNRS INC3M, UFR des Sciences Pharmaceutiques, Bd Becquerel, 14032 Caen Cedex, France
Fax: +33(2)31566803; e-Mail: valerie.collot@unicaen.fr ;
Further Information

Publication History

Received 21 April 2011
Publication Date:
21 July 2011 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

An efficient synthesis of various N-substituted 3-aminoindazoles using Buchwald-Hartwig C-N coupling reaction is described. Several parameters were varied, including the nature of the halogen atom and the protecting group of the starting materials, as well as the effects of the catalyst system, base, solvent, and reaction time. The efficiency of microwave versus conventional heating was also compared to test the outcome of the reaction. Thus, by applying this recent knowledge about metal-catalyzed aminations, an alternative for the direct synthesis of primary 3-aminoindazoles has been provided.

Key words

indazoles - amination - cross-coupling - palladium - copper - microwave promoted amination

    References

  • 1 Crestey F. Stiebing S. Legay R. Collot V. Rault S. Tetrahedron  2007,  63:  419 
    CrossrefSearch in Google Scholar
  • 2a Crestey F. Collot V. Stiebing S. Rault S. Synthesis  2006,  3506 
  • 2b Crestey F. Collot V. Stiebing S. Rault S. Tetrahedron  2006,  62:  7772 
    Search in Google Scholar
  • 2c Crestey F. Collot V. Stiebing S. Lohier J.-F. Sopkova-de Oliveira Santos J. Rault S. Tetrahedron Lett.  2007,  48:  2457 
    Search in Google Scholar
  • 3a Stocks MJ. Barber S. Ford R. Leroux F. St-Gallay S. Teague S. Xue Y. Bioorg. Med. Chem. Lett.  2005,  15:  3459 
    Search in Google Scholar
  • 3b Dai Y. Hartandi K. Ji Z. Ahmed AA. Albert DH. Bauch JL. Bouska JJ. Bousquet PF. Cunha GA. Glaser KB. Harris CM. Hickman D. Guo J. Li J. Marcotte PA. Marsh KC. Moskey MD. Martin RL. Olson AM. Osterling DJ. Pease LJ. Soni NB. Stewart KD. Stoll VS. Tapang P. Reuter DR. Davidsen SK. Michaelides MR. J. Med. Chem.  2007,  50:  1584 
    Search in Google Scholar
  • 3c Lee J. Choi H. Kim K.-H. Jeong S. Park J.-W. Baek C.-S. Lee S.-H. Bioorg. Med. Chem. Lett.  2008,  18:  2292 
    Search in Google Scholar
  • 3d Raffa D. Maggio B. Cascioferro S. Raimondi MV. Schillaci D. Gallo G. Daidone G. Plescia S. Meneghetti F. Bombieri G. Di Cristina A. Pipitone RM. Grimaudo S. Tolomeo M. Eur. J. Med. Chem.  2009,  44:  165 
    Search in Google Scholar
  • 3e Antonysamy S. Hirst G. Park F. Sprengeler P. Stappenbeck F. Steensma R. Wilson M. Wong M. Bioorg. Med. Chem. Lett.  2009,  19:  279 
    Search in Google Scholar
  • 4 Kaltenbach RF. Patel M. Waltermire RE. Harris GD. Stone BRP. Klabe RM. Garber S. Bacheler LT. Cordova BC. Logue K. Wright MR. Erickson-Viitanen S. Trainor GL. Bioorg. Med. Chem. Lett.  2003,  13:  605 
    CrossrefPubMedSearch in Google Scholar
  • 5 Vasudevan A. Souers AJ. Freeman JC. Verzal MK. Gao J. Mulhern MM. Wodka D. Lynch JK. Engstrom KM. Wagaw SH. Broddjian S. Dayton B. Falls DH. Bush E. Brune M. Shapiro RD. Marsh KC. Hernandez LE. Collins CA. Kym PR. Bioorg. Med. Chem. Lett.  2005,  15:  5293 
    CrossrefSearch in Google Scholar
  • 6 Clutterbuck LA. Posada CG. Visintin C. Riddall DR. Lancaster B. Gane PJ. Garthwaite J. Selwood DL. J. Med. Chem.  2009,  52:  2694 
    CrossrefSearch in Google Scholar
  • 7a Moore PK. Wallace P. Gaffen Z. Hart SL. Babbedge RC. Br. J. Pharmacol.  1993,  110:  219 
    Search in Google Scholar
  • 7b Babbedge RC. Bland-Ward PA. Hart SL. Moore PK. Br. J. Pharmacol.  1993,  110:  225 
    Search in Google Scholar
  • 7c Elguero J. Alkorta I. Claramunt RM. Lopez C. Sanz D. Santa María D. Bioorg. Med. Chem.  2009,  17:  8027 
    Search in Google Scholar
  • 7d Manzanedo C. Aguilar MA. Ribeiro Do Coutob B. Rodríguez-Arias M. Minarro J. Neurosci. Lett.  2009,  464:  67 
    Search in Google Scholar
  • 8 Boulouard M. Schumann-Bard P. Butt-Gueulle S. Lohou E. Stiebing S. Collot V. Rault S. Bioorg. Med. Chem. Lett.  2007,  17:  3177 
    CrossrefSearch in Google Scholar
  • 9a Sanger GJ. Nelson DR. Eur. J. Pharmacol.  1989,  159:  113 
    Search in Google Scholar
  • 9b Joshi PR. Suryanarayanan A. Hazai E. Schulte MK. Maksay G. Bikadi Z. Biochemistry  2006,  45:  1099 
    Search in Google Scholar
  • 9c Abdelsayed GG. Exp. Hematol.  2007,  35:  34 
    Search in Google Scholar
  • 9d Tuca A. Cancer Management Res.  2010,  2:  1 
    Search in Google Scholar
  • 10a Kharitonov VG. Sharma VS. Magde D. Koesling D. Biochemistry  1999,  38:  10699 
    Search in Google Scholar
  • 10b Collot V. Dallemagne P. Bovy PR. Rault S. Tetrahedron  1999,  55:  6917 
    Search in Google Scholar
  • 10c Bredt SD. Mol. Pharm.  2003,  63:  1206 
    Search in Google Scholar
  • 10d Hering KW. Artz JD. Pearson WH. Marletta MA. Bioorg. Med. Chem. Lett.  2006,  16:  618 
    Search in Google Scholar
  • 10e Wu SY. Pan SL. Chen TH. Liao CH. Huang DY. Guh JH. Chang YL. Kuo SC. Lee FY. Teng CM. Br. J. Pharmacol.  2008,  155:  505 
    Search in Google Scholar
  • 10f Keswani AN. Peyton KJ. Durante W. Schafer AI. Tulis DA. J. Cardiovasc. Pharmacol. Ther.  2009,  14:  116 
    Search in Google Scholar
  • 11 Giorgioni G. Ruggieri S. Di Stefano A. Sozio P. Cinque B. Di Marzio L. Santoni G. Claudi F. Bioorg. Med. Chem. Lett.  2008,  18:  2445 
    CrossrefSearch in Google Scholar
  • 12a Collot V. Bovy PR. Rault S. Tetrahedron Lett.  2000,  41:  9053 
    Search in Google Scholar
  • 12b Crestey F. Lohou E. Stiebing S. Collot V. Rault S. Synlett  2009,  615 
  • 13a Collot V. Varlet D. Rault S. Tetrahedron Lett.  2000,  41:  4363 
    Search in Google Scholar
  • 14a Arnautu A. Collot V. Calvo Ros J. Alayrac C. Witulski B. Rault S. Tetrahedron Lett.  2002,  43:  2695 
    Search in Google Scholar
  • 14b Witulski B. Azcon JR. Alayrac C. Arnautu A. Collot V. Rault S. Synthesis  2005,  771 
  • 15 Bouchet P. Lazaro R. Benchidmi M. Elguero J. Tetrahedron  1980,  36:  3523 
    CrossrefSearch in Google Scholar
  • 16 Burke MJ. Trantow BM. Tetrahedron Lett.  2008,  49:  4579 
    CrossrefSearch in Google Scholar
  • 17a Kaltenbach RF. Klabe RM. Cordova BC. Seitz SP. Bioorg. Med. Chem. Lett.  1999,  9:  2259 
    Search in Google Scholar
  • 17b Lukin K. Hsu MC. Fernando D. Leanna MR. J. Org. Chem.  2006,  71:  8166 
    Search in Google Scholar
  • 17c Orsini P. Menichincheri M. Vanotti E. Panzeri A. Tetrahedron Lett.  2009,  50:  3098 
    Search in Google Scholar
  • 18 Kruger AW. Rozema MJ. Chu-Kung A. Gandarilla J. Haight AR. Kotecki BJ. Richter SM. Schwartz AM. Wang Z. Org. Process Res. Dev.  2009,  13:  1419 
    CrossrefSearch in Google Scholar
  • 19 Candiani I. D’Arasmo G. Heidempergher F. Tomasi A. Org. Process Res. Dev.  2009,  13:  456 
    CrossrefSearch in Google Scholar
  • 20a Leroy V. Lee GE. Lin J. Herman SH. Lee TB. Org. Process Res. Dev.  2001,  5:  179 
    Search in Google Scholar
  • 20b Watson TJ. Ayers TA. Shah N. Wenstrup D. Webster M. Freund D. Horgan S. Carey JP. Org. Process Res. Dev.  2003,  7:  521 
    Search in Google Scholar
  • For Buchwald-Hartwig C-N coupling, see:
  • 21a Hartwig JF. Angew. Chem., Int. Ed. Engl.  1998,  37:  2046 
    Search in Google Scholar
  • 21b Yang B. Buchwald SL. J. Organomet. Chem.  1999,  576:  125 
    Search in Google Scholar
  • 21c Wolfe JP. Buchwald SL. J. Org. Chem.  2000,  65:  1144 
    Search in Google Scholar
  • 21d Wolfe JP. Tomori H. Sadighi JP. Yin J. Buchwald SL. J. Org. Chem.  2000,  65:  1158 
    Search in Google Scholar
  • 21e Ali MH. Buchwald SL. J. Org. Chem.  2001,  66:  2560 
    Search in Google Scholar
  • 21f Muci AR. Buchwald SL. Top. Curr. Chem.  2002,  219:  131 
    Search in Google Scholar
  • 21g Littke AF. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  4176 
    Search in Google Scholar
  • 21h Martin R. Rivero MR. Buchwald SL. Angew. Chem. Int. Ed.  2006,  45:  7079 
    Search in Google Scholar
  • 21i Kienle M. Dubbaka SR. Brade K. Knochel P. Eur. J. Org. Chem.  2007,  4166 
  • 21j Fors BP. Watson DA. Biscoe MR. Buchwald SL. J. Am. Chem. Soc.  2008,  130:  13552 
    Search in Google Scholar
  • 21k Surry DS. Buchwald SL. Angew. Chem. Int. Ed.  2008,  47:  6338 
    Search in Google Scholar
  • 21l Hartwig JF. Acc. Chem. Res.  2008,  41:  1534 
    Search in Google Scholar
  • 21m Fors BP. Davis NR. Buchwald SL. J. Am. Chem. Soc.  2009,  131:  5766 
    Search in Google Scholar
  • 22a Ley SV. Thomas AW. Angew. Chem. Int. Ed.  2003,  42:  5400 
    Search in Google Scholar
  • 22b Evano G. Blanchard N. Toumi M. Chem. Rev.  2008,  108:  3054 
    Search in Google Scholar
  • 22c Monnier F. Taillefer M. Angew. Chem. Int. Ed.  2009,  48:  6954 
    Search in Google Scholar
  • For a few examples of applications of metal-catalyzed amination to heterocyclic compounds, see:
  • 23a Wagaw S. Buchwald SL. J. Org. Chem.  1996,  61:  7240 
    Search in Google Scholar
  • 23b Nishiyama M. Yamamoto T. Koie Y. Tetrahedron Lett.  1998,  39:  617 
    Search in Google Scholar
  • 23c Hooper MW. Utsunomiya M. Hartwig JF. J. Org. Chem.  2003,  68:  2861 
    Search in Google Scholar
  • 23d Enguehard C. Allouchi H. Gueiffier A. Buchwald SL. J. Org. Chem.  2003,  68:  4367 
    Search in Google Scholar
  • 23e Enguehard C. Allouchi H. Gueiffier A. Buchwald SL. J. Org. Chem.  2003,  68:  5614 
    Search in Google Scholar
  • 23f Ferreira ICFR. Queiroz M.-JRP. Kirsch G. Tetrahedron  2003,  59:  975 
    Search in Google Scholar
  • 23g Enguehard-Gueiffier C. Thery I. Gueiffier A. Buchwald SL. Tetrahedron  2006,  62:  6042 
    Search in Google Scholar
  • 23h Peng Z.-H. Journet M. Humphrey G. Org. Lett.  2006,  8:  395 
    Search in Google Scholar
  • 23i Calhelha RC. Queiroz M.-JRP. Tetrahedron Lett.  2010,  51:  281 
    Search in Google Scholar
  • 23j Das AR. Medda A. Singha R. Tetrahedron Lett.  2010,  51:  1099 
    Search in Google Scholar
  • 24a Santhakumar V, and Tomaszewski M. inventors; Patent WO  2006/0052190.  ; Chem. Abstr. 2006, 144, 488650
  • 24b Hisanori I, Takeshi I, and Yoshimasa M. inventors; US Patent  2008/0036373.  ; Chem. Abstr. 2008, 148, 272551
  • 25a Cooper AB, and Deng Y. inventors; US Patent  2009/0118284.  ; Chem. Abstr. 2009, 150, 515160
  • 26a Bartsch RA. Yang IW. J. Heterocycl. Chem.  1984,  21:  1063 
    Search in Google Scholar
  • 26b Schumann P. Collot V. Hommet Y. Gsell W. Dauphin F. Sopkova J. MacKenzie E. Duval D. Boulouard M. Rault S. Bioorg. Med. Chem. Lett.  2001,  11:  1153 
    Search in Google Scholar
  • 27a Bocchi V. Palla G. Synthesis  1982,  1096 
  • 28a Robins RK. Godefroi EF. Taylor EC. Lewis LR. Jackson A. J. Am. Chem. Soc.  1961,  83:  2574 
    Search in Google Scholar
  • 28b Sun J.-H. Teleha CA. Yan J.-S. Rodgers JD. Nugiel DA. J. Org. Chem.  1997,  62:  5627 
    Search in Google Scholar
  • 29a Kappe CO. Angew. Chem. Int. Ed.  2004,  43:  6250 
    Search in Google Scholar
  • 30a Maes BUW. Loones KTJ. Hostyn S. Dielsb G. Rombouts G. Tetrahedron  2004,  60:  11559 
    Search in Google Scholar
  • 30b Heo J.-N. Song YS. Kim BT. Tetrahedron Lett.  2005,  46:  4621 
    Search in Google Scholar
  • 31 Jiang L. Lu X. Zhang H. Jiang Y. Ma D. J. Org. Chem.  2009,  74:  4542 
    CrossrefSearch in Google Scholar
  • 32 Yeh VSC. Wiedeman PE. Tetrahedron Lett.  2006,  47:  6011 
    CrossrefSearch in Google Scholar
  • 33 Kranenburg M. van der Burgt YEM. Kamer PCJ. van Leeuwen PWNM. Organometallics  1995,  14:  3081 
    CrossrefSearch in Google Scholar
  • 34a Yin J. Buchwald SL. Org. Lett.  2000,  2:  1101 
    Search in Google Scholar
  • 34b Queiroz M.-JRP. Calhelhaa RC. Kirsch G. Tetrahedron  2007,  63:  13000 
    Search in Google Scholar
  • 34c Audisio D. Messaoudi S. Peyrat J.-F. Brion J.-D. Alami M. Tetrahedron Lett.  2007,  48:  6928 
    Search in Google Scholar
  • 35a Röder JC. Meyer F. Pritzkow H. Organometallics  2001,  20:  811 
    Search in Google Scholar
  • 35b Röder JC. Meyer F. Winter RF. Kaifer E. J. Organomet. Chem.  2002,  641:  113 
    Search in Google Scholar
  • 35c Gérard A.-L. Bouillon A. Mahatsekake C. Collot V. Rault S. Tetrahedron Lett.  2006,  47:  4665 
    Search in Google Scholar
  • 36 Lefebvre V. Cailly T. Fabis F. Rault S. J. Org. Chem.  2010,  75:  2730 
    CrossrefSearch in Google Scholar
  • 37a Wolfe JP. Ahman J. Sadighi JP. Singer RA. Buchwald SL. Tetrahedron Lett.  1997,  38:  6367 
    Search in Google Scholar
  • 37b Singer RA. Buchwald SL. Tetrahedron Lett.  1999,  40:  1095 
    Search in Google Scholar
  • 37c Grasa GA. Viciu MS. Huang J. Nolan SP. J. Org. Chem.  2001,  66:  7729 
    Search in Google Scholar
  • 37d Bhagwanth S. Adjabeng GM. Hornberger KR. Tetrahedron Lett.  2009,  50:  1582 
    Search in Google Scholar