Gold(I)-catalyzed heterocyclization of β-alkynyl hydroxamic acids: synthesis of isoxazolidin-3-ones

Abstract

A practical and mild method for the 5-exo cyclization of N-substituted α-alkynyl hydroxamic acids into isoxazolidin-3-ones catalyzed by Au(PPh3)SbF6 was developed. Under optimized conditions, the cyclization shows a high Z-selectivity for the newly formed exocyclic double bond.

Graphical Abstract

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Fig. 1
Fig. 2

Notes

  1. 1.

    10 mol% of Au(PPh3)Cl and 5 mol% of AgSbF6 were mixed in methylene chloride and stirred for 10 min. The suspension was filtered through Celite and the filtrate was added to a solution of the starting material.

  2. 2.

    Details of the single crystal X-ray diffraction measurement of 19a and 20b (CCDC 1008262 and 1008263) are given in the supporting information to this article.

  3. 3.

    Due to slow decomposition of the N-alkyl hydroxamic acids in the presence of silica gel, rapid chromatography was essential to obtain pure material. Further attempts to purify the compounds by chromatography over aluminium oxides with different acidity failed and led to complete decomposition.

References

  1. 1.

    Tacheuchi Y (1977) Adv Heterocycl Chem 21:207

    Article  Google Scholar 

  2. 2.

    Michelot D, Melendez-Howell LM (2003) Mycol Res 107:131

    CAS  Article  Google Scholar 

  3. 3.

    Harada S, Tsubotani S, Hida T, Koyama K, Kondo M, Ono H (1988) Tetrahedron Lett 44:6589

    CAS  Article  Google Scholar 

  4. 4.

    Neuhaus FC (1967) In: Gottlieb D, Shaw PD (eds) Antibiotics, vol 1. Springer, Berlin, p 40

    Google Scholar 

  5. 5.

    Stammer CH (1971) Chem Biochem Amino Acids Pept Proteins 1:23

    Google Scholar 

  6. 6.

    Fang QK, Hopkins S, Jones S (2005) Benzo[d]isoxazol-3-ol DAAO Inhibitors. US Patent 20050143434, Jun 30, 2005; (2005). Chem Abstr 143:97345

    Google Scholar 

  7. 7.

    Kennis LJE, van Hoof GCP, Bongartz JPAM, Luyckx MGM, Minke WE (2005) Daao inhibiting benzisoxazoles and their use for the treatment of mental disorders. WO2005/089753, Sep 29, 2005; (2005). Chem Abstr 143:326349

    Google Scholar 

  8. 8.

    Ferraris D, Duvall B, Ko YS, Thomas AG, Rojas C, Majer P, Hashimoto K, Tsukamoto T (2008) J Med Chem 51:3357

    CAS  Article  Google Scholar 

  9. 9.

    Smith SM, Uslaner JM, Hutson PH (2010) Open Med Chem J 4:3

    CAS  Article  Google Scholar 

  10. 10.

    Krogsgaard-Larsen P, Nielsen L, Falch E, Curtis DR (1985) J Med Chem 28:1612

    CAS  Article  Google Scholar 

  11. 11.

    Silverman RB, Olson GT (1995) Bioorg Med Chem 3:11

    CAS  Article  Google Scholar 

  12. 12.

    Conti P, De Amici M, Pinto A, Tamborini L, Grazioso G, Frølund B, Nielsen B, Thomsen C, Ebert B, De Micheli C (2006) Eur J Org Chem 5533

  13. 13.

    Watanabe M, Maemura K, Kanbara K, Tamayama T, Hayasaki H (2002) Int Rev Cyctology 213:1

    CAS  Article  Google Scholar 

  14. 14.

    Hall IH, Izydore RA (1988) Isoxazolidine-3,5-diones in the treatment of hyperlipidemia. EP0321090A2, Jun 21, 1989; (1990) Chem Abstr 112:178946

  15. 15.

    Milner PG (2002) Isoxazolidine compounds useful in the treatment of diabetes, hyperlipidemia, and atherosclerosis. WO2002024689A1, Mar 28, 2002; (2002) Chem Abstr 136:257265

  16. 16.

    Hobbs SH (1991) Preparation of substituted oxazolidin-2-ones and 1,2,4-oxadiazolin-5-ones as muscarinic agents. US Patent 5,066,665, Nov 19, 1991. Chem Abstr 116:59358

    Google Scholar 

  17. 17.

    Dallanoce C, Magrone P, Matera C, Frigerio F, Grazioso G, De Amici M, Fucile S, Piccari V, Frydenvang K, Pucci L, Gotti C, Clementi F, De Michel C (2011) ChemMedChem 6:889

    CAS  Article  Google Scholar 

  18. 18.

    Chang JH (1983) Herbicidal 3-isoxazolidinones ans hydroxamic acids. US Patent 4,405,357, Sep 20, 1983; (1984). Chem Abstr 100:34529

    Google Scholar 

  19. 19.

    Warfield TR, Carlson DB, Bellman SK, Guscar HL (1985) Weed Sci Abstr 25:105

    Google Scholar 

  20. 20.

    Warfield TR, Halvorson GC, Dobbins LD, Hopper DM (1985) NCWCC Proc 40:80

    Google Scholar 

  21. 21.

    Baker DR, Fenyes WK, Morberg WK (1987) In: Cross B (ed) Synthesis and chemistry of agrochemicals. American Chemical Society, Washington DC, p 10

    Google Scholar 

  22. 22.

    Konz MJ (1981) Herbicidal isoxazolidine-3,5-diones. US Patent 4,302,238, Nov 24, 1981; (1982). Chem Abstr 96:217824

    Google Scholar 

  23. 23.

    Yun S, Kim K (2000) Tetrahedron Lett 41:1469

    CAS  Article  Google Scholar 

  24. 24.

    Zydore RA, Hall IH (1990) Compounds for the control of hyperlipidemia using N-substituted isoxazolidine-3,5-diones. US Patent 4,946,963, Aug 7, 1990; (1990). Chem Abstr 112:178946

    Google Scholar 

  25. 25.

    Reddy AS, Kumar MS, Reddy GR (2000) Tetrahedron Lett 41:6285

    CAS  Article  Google Scholar 

  26. 26.

    Li X, Meng X, Duan H, Wang L, Wang S, Zhang Y, Qin D (2010) Arch Pharm Chem Life Sci 8:473

    Article  Google Scholar 

  27. 27.

    Kim HK, Park KJJ (2012) Tetrahedron Lett 53:4090

    CAS  Article  Google Scholar 

  28. 28.

    Kim HR, Shin SI, Park HJ, Jeon DJ, Ryu EK (1998) Synlett 789

  29. 29.

    Fiumana A, Lombardo M, Trombini C (1997) J Org Chem 62:5623

    CAS  Article  Google Scholar 

  30. 30.

    Mancini F, Piazza MG, Trombini C (1991) J Org Chem 56:4246

    CAS  Article  Google Scholar 

  31. 31.

    Dhavale DD, Gentilucci L, Piazza MG, Trombini C (1992) Liebigs Ann Chem 12:1289

    Article  Google Scholar 

  32. 32.

    Westphalen KO, Hamprecht G, Hettinger P (1987) Preparation of dialkylisoxazolidinones as intermediates for herbicides. DE 3540770, May 21, 1987; (1987) Chem Abstr 107:154321

  33. 33.

    Wang J, Stefane B, Jaber D, Smith JAI, Vickery C, Diop M, Sintim HO (2010) Angew Chem Int Ed 49:3964

    CAS  Article  Google Scholar 

  34. 34.

    Schmidt VA, Alexanian EJ (2010) Angew Chem Int Ed 49:4491

    CAS  Article  Google Scholar 

  35. 35.

    Hashmi ASK (2010) Pure Appl Chem 82:657

    CAS  Google Scholar 

  36. 36.

    Shen HC, Graham TH (2013) Drug Discov Today 10:e3

    Article  Google Scholar 

  37. 37.

    Fürstner A, Davies PW (2007) Angew Chem Int Ed 46:3410

    Article  Google Scholar 

  38. 38.

    Hashmi ASK (2007) Chem Rev 107:3180

    CAS  Article  Google Scholar 

  39. 39.

    Leyva-Pérez A, Corma A (2012) Angew Chem Int Ed 51:614

    Article  Google Scholar 

  40. 40.

    Patil NT, Yamamoto Y (2008) Chem Rev 108:3395

    CAS  Article  Google Scholar 

  41. 41.

    Klahn P, Duschek A, Liébert C, Kirsch SF (2012) Org Lett 14:1250

    CAS  Article  Google Scholar 

  42. 42.

    Umland KD, Palisse A, Haug TT, Kirsch SF (2011) Angew Chem Int Ed 50:9965

    CAS  Article  Google Scholar 

  43. 43.

    Harschneck T, Kirsch SF (2011) J Org Chem 76:2145

    CAS  Article  Google Scholar 

  44. 44.

    Menz H, Binder JT, Crone B, Duschek A, Haug TT, Kirsch SF, Klahn P, Liébert C (2009) Tetrahedron 65:1880

    CAS  Article  Google Scholar 

  45. 45.

    Haug TT, Harschneck T, Duschek A, Lee CU, Binder JT, Menz H, Kirsch SF (2009) J Organomet Chem 694:510

    CAS  Article  Google Scholar 

  46. 46.

    Baskar B, Bae HJ, An SE, Cheong JY, Rhee YH, Duschek A, Kirsch SF (2008) Org Lett 10:2605

    CAS  Article  Google Scholar 

  47. 47.

    Binder JT, Crone B, Kirsch SF, Liébert C, Menz H (2007) Eur J Org Chem 1636

  48. 48.

    Kirsch SF, Binder JT, Crone B, Duschek A, Haug TT, Liébert C, Menz H (2007) Angew Chem Int Ed 46:2310

    CAS  Article  Google Scholar 

  49. 49.

    Kirsch SF, Binder JT, Liébert C, Menz H (2006) Angew Chem Int Ed 45:5878

    CAS  Article  Google Scholar 

  50. 50.

    Menz H, Kirsch SF (2006) Org Lett 8:4795

    CAS  Article  Google Scholar 

  51. 51.

    Zhu ZB, Kirsch SF (2013) Chem Commun 49:2272

    CAS  Article  Google Scholar 

  52. 52.

    Hummel S, Kirsch SF (2011) Beilstein J Org Chem 7:847

    CAS  Article  Google Scholar 

  53. 53.

    Haug TT, Kirsch SF (2009) Targets in Heterocycl Syst 13:57

    CAS  Google Scholar 

  54. 54.

    Klahn P, Kirsch SF (2011) ChemCatChem 3:649

    CAS  Article  Google Scholar 

  55. 55.

    Kirsch SF (2008) Synthesis 3183

  56. 56.

    Crone B, Kirsch SF (2008) Chem Eur J 14:3514

    CAS  Article  Google Scholar 

  57. 57.

    Cahiez G, Gager O, Buendia J (2010) Angew Chem Int Ed 49:1278

    CAS  Article  Google Scholar 

  58. 58.

    Yang CY, Lin GY, Liao HY, Datta S, Liu RSJ (2008) Org Chem 73:4907

    CAS  Article  Google Scholar 

  59. 59.

    Ohemeng KA, Podlogar BL, Nguyen VN, Bernstein JI, Krause HM, Hilliard JJ, Barret JFJ (1997) Med Chem 40:3292

    CAS  Article  Google Scholar 

  60. 60.

    Kawase M, Kikugawa Y (1979) J Chem Soc Perkin Trans 1:643

    Article  Google Scholar 

  61. 61.

    High A, Prior T, Bell RA, Rangachari PKJ (1999) Pharm Exp Therp 288:490

    CAS  Google Scholar 

  62. 62.

    Eckelbarger JD, Schmitzer PR, Yerkes CN, Boebel TA, Satchivi NM, Whiteker GT (2010) N-Alkoxyamides of 6-(trisubstituted phenyl)-4-aminopicolinates and their use as selective herbicides for crops. US Patent 20100222221, Sep 2, 2010; (2010). Chem Abstr 153:359051

    Google Scholar 

  63. 63.

    Pangborn AB, Giardello MA, Grubbs RH, Rosen RK, Timmers FJ (1996) Organometallics 15:1518

    CAS  Article  Google Scholar 

  64. 64.

    Yang CY, Lin GY, Liao HY, Datta S, Liu RS (2008) J Org Chem 73:4907

    CAS  Article  Google Scholar 

  65. 65.

    Cheoljae K, Hyo JB, Ji HL, Wook J, Haejin K, Sampath V, Young HR (2009) J Am Chem Soc 131:14660

    Article  Google Scholar 

  66. 66.

    Coskun N, Parlar A (2005) Synth Commun 35:2445

    CAS  Article  Google Scholar 

  67. 67.

    Gopalakrishnan M, Anandabaskaran T, Sureshkumar P, Thanusu J, Kumaran AK, Kanagarajan V (2006) Mendeleev Commun 16:50

    Article  Google Scholar 

  68. 68.

    Hayashi D, Kato N, Kuzuyama T, Sato Y, Ohkanda J (2013) Chem Commun 49:5535

    CAS  Article  Google Scholar 

  69. 69.

    Brady OL, Bennett CL (1927) J Chem Soc 894

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Acknowledgments

We are grateful to Deutsche Forschungsgemeinschaft (DFG; KI 1289/1–3) and Fonds der Chemischen Industrie (FCI) for financial support. The donation of chemicals by Rockwood Lithium is gratefully acknowledged.

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Correspondence to Stefan F. Kirsch.

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Häring, A.P., Klahn, P., Jübermann, M. et al. Gold(I)-catalyzed heterocyclization of β-alkynyl hydroxamic acids: synthesis of isoxazolidin-3-ones. Monatsh Chem 146, 119–134 (2015). https://doi.org/10.1007/s00706-014-1319-1

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Keywords

  • Isoxazolidin-3-ones
  • Heterocycles
  • Catalysis
  • Cyclizations
  • Hydroxamic acid