Synlett 2015; 26(03): 331-334
DOI: 10.1055/s-0034-1379540
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© Georg Thieme Verlag Stuttgart · New York

Iron-Catalyzed C–N Bond Formation via the Beckmann Rearrangement

Latisha R. Jefferies
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, IN 47405-7102, USA   Email: sicook@indiana.edu
,
Savannah R. Weber
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, IN 47405-7102, USA   Email: sicook@indiana.edu
,
Silas P. Cook*
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, IN 47405-7102, USA   Email: sicook@indiana.edu
› Author Affiliations
Further Information

Publication History

Received: 20 September 2014

Accepted after revision: 21 October 2014

Publication Date:
20 November 2014 (eFirst)

Abstract

A simple, iron-based catalytic system allows for facile Beckmann rearrangement of various oximes. The mild conditions avoid the use of harsh or expensive acids, and the reactions do not require an ­inert atmosphere. Additionally, a range of amides can be accessed through this transformation.

Supporting Information

 
  • References and Notes

  • 1 Hendrickson JB, Cram DJ, Hammond GS. Organic Chemistry . 3rd ed. McGraw-Hill; Tokyo: 1970: 708
  • 2 White JD, Hrnciar P, Stappenbeck F. J. Org. Chem. 1999; 64: 7871
  • 3 White JD, Choi Y. Org. Lett. 2000; 2: 2373
  • 4 Smith BT, Wendt JA, Aubé J. Org. Lett. 2002; 4: 2577
  • 5 Beckmann E. Ber. Dtsch. Chem. Ges. 1886; 19: 988
  • 6 Kaur N, Sharma P, Kishore D. J. Chem. Pharm. Res. 2012; 4: 1938
  • 7 Ghiaci M, Imanzadeh GH. Synth. Commun. 1998; 28: 2275
  • 8 An N, Pi H, Liu L, Du W, Deng W. Chin. J. Chem. 2011; 29: 947
  • 9 Sugamoto K, Matsushita Y.-i, Matsui T. Synth. Commun. 2011; 41: 879
    • 10a Thomas B, Sugunan S. Microporous Mesoporous Mater. 2006; 96: 55
    • 10b Priya SV, Mabel JH, Palanichamy M, Murugesan V. Studies in Surface Science and Catalysis . Vol. 174, Part B. Antoine Gédéon PM, Florence B. Elsevier; Amsterdam: 2008: 1147
  • 11 Augustine JK, Kumar RA, Bombrun A, Mandal AB. Tetrahedron Lett. 2011; 52: 1074
  • 12 Khodaei MM, Meybodi FA, Rezai N, Salehi P. Synth. Commun. 2001; 31: 2047
  • 13 Jefferies LR, Cook SP. Org. Lett. 2014; 16: 2026
  • 14 Jefferies LR, Cook SP. Tetrahedron 2014; 70: 4204
  • 15 Yamabe S, Tsuchida N, Yamazaki S. J. Org. Chem. 2005; 70: 10638
  • 16 Iron-Catalyzed Beckmann Rearragnment; General Procedure: To an oven-dried 20 mL vial containing FeCl3 (24.3 mg, 0.15 equiv), was added a solution of oxime (1 mmol) in DCE (10 mL) and the mixture was stirred until FeCl3 was completely dissolved (10–15 min). To this solution was added AgSbF6 (154.6 mg, 0.45 equiv), then the vial was capped and put into mechanical shaker at 80 °C for 24 h. The mixture was filtered through Celite with CH2Cl2 (100 mL) and concentrated to give a residue, which was purified by silica flash chromatography using hexanes and ethyl acetate in appropriate combination based on the Rf of the desired product.