Download PDF
Synlett 2011(1): 81-83  
DOI: 10.1055/s-0030-1259090
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Direct Conversion of Olefins into α-Bromo Ketones Using O-Iodoxybenzoic Acid and Tetraethylammonium Bromide

Swapnil S. Deshmukh, Kiran H. Chaudhari, Krishnacharya G. Akamanchi*
Department of Pharmaceutical Sciences and Technology, Institute of Chemical Technology, Matunga, Mumbai 400019, India
Further Information

Publication History

Received 8 July 2010
Publication Date:
07 December 2010 (online)

    Permissions and Reprints All articles of this category

Corrected by:

Direct Conversion of Olefins into α-Bromo Ketones Using O-Iodoxybenzoic Acid and Tetraethylammonium BromideSynlett 2011; 2011(01): e1-e1
DOI: 10.1055/s-0030-1259279

Abstract

Utilizing full potential of IBX, a mild, selective, and facile method has been developed for the direct conversion of olefins into the corresponding α-bromo ketones by using 1.1 equivalents each of o-iodoxybenzoic acid and tetraethylammonium bromide.

Key words

o-iodoxybenzoic acid - tetraethylammonium bromide - α-bromo ketone

    References and Notes

  • 1a Marek A. Kulhanek J. Ludwig M. Bures F. Molecules  2007,  12:  1183 
    Google Scholar
  • 1b Loughlin WA. Aust. J. Chem.  1998,  51:  875 
    Google Scholar
  • 1c Hantzsch A. Weber JH. Ber. Dtsch. Chem. Ges.  1887,  20:  3118 
    Google Scholar
  • 2a Cho J. Kim K. J. Heterocycl. Chem.  1992,  29:  1433 
    Google Scholar
  • 2b Reddy VV. Sampath RP. Ashok D. Synth. Commun.  2000,  30:  1825 
    Google Scholar
  • 2c Habermann J. Ley SV. Scicinski JJ. Scott JS. J. Chem. Soc., Perkin Trans. 1  1999,  2524 
    Google Scholar
  • 2d Waly MA. Acta Chim. Slov.  2008,  55:  343 
    Google Scholar
  • 3 Katritzky AR. Pozharskii AF. Handbook of Heterocyclic Chemistry   2nd ed.:  Pergamon; New York: 2000. 
    Google Scholar
  • 4 Morton HE. Leanna MR. Tetrahedron Lett.  1993,  34:  4481 
    CrossrefGoogle Scholar
  • 5 Motohanshi S. Satomi M. Fujimoto Y. Tatsuno T. Synthesis  1982,  1021 
    Article in Thieme ConnectGoogle Scholar
  • 6 Kageyama T. Tobito Y. Katoh A. Ueno Y. Okawara M. Chem. Lett.  1983,  12:  1481 
    CrossrefGoogle Scholar
  • 7 Moriuchi T. Yamaguchi M. Kikushima K. Hirao T. Tetrahedron Lett.  2007,  48:  2667 
    CrossrefGoogle Scholar
  • 8 Moorthy JS. Senapati K. Singhal N. Tetrahedron Lett.  2009,  50:  2493 
    CrossrefGoogle Scholar
  • 9 Yadav JS. Reddy BVS. Singh AP. Basak AK. Tetrahedron Lett.  2008,  49:  5880 
    CrossrefGoogle Scholar
  • 10 Ramnarayanan GV. Shukla VG. Akamanchi KG. Synlett  2002,  2059 
    Article in Thieme ConnectGoogle Scholar
  • 11 Shukla VG. Salgaonkar PD. Akamanchi KG. J. Org. Chem.  2003,  68:  5422 
    CrossrefPubMedGoogle Scholar
  • 12a Bhalerao DS. Mahajan US. Chaudhari KH. Akamanchi KG. J. Org. Chem.  2007,  72:  662 
    Google Scholar
  • 12b Bellale EV. Bhalerao DS. Akamanchi KG. J. Org. Chem.  2008,  73:  9473 
    Google Scholar
  • 13a Dictionary of Organic Compounds   6th ed.:  Chapman and Hall Electronic Publishing House; London: 1996. 
    Google Scholar
  • 13b Dubois J.-E. El-Alaoui M. Toullec J. J. Am. Chem. Soc.  1981,  103:  5393 
    Google Scholar
  • 14a Kajigaeshi S. Kakinami T. Okamoto T. Fujisaki S. Bull. Chem. Soc. Jpn.  1987,  60:  1159 
    Google Scholar
  • 14b Gerta C. Williams JMJ. Synlett  2003,  124 
    Google Scholar
  • 15a Illig C, Subasinghe N, Hoffman J, Wilson K, Rudolph M, and Marugan J. inventors; US 2002/37915  (A1). 
  • 15b Andrew PT. Allott CP. Gibson KH. Major JS. Masek BB. Oldham AA. Ratcliffe AH. Roberts DA. Russell ST. Thomason DA. J. Med. Chem.  1992,  35:  877 
    Google Scholar
  • 15c Roland H. Helv. Chim. Acta  1987,  70:  1955 
    Google Scholar
16

General Experimental Procedure for Direct Conversion of Olefins into α-Bromo Ketones
To a stirred suspension of IBX (5.5 mmol) and TEAB (5.5 mmol) in anhydrous CH2Cl2 was added the olefine (5 mmol). Within 5-15 min the reaction mixture turned from yellow to colorless and homogeneous, indicating completion of reaction (monitored by TLC). The reaction mixture was diluted with CH2Cl2 (25 mL) and washed with sat. NaHCO3 (2 × 25 mL), followed by NaHSO3 (25 mL), and brine (25 mL). The organic layer was separated, dried over anhyd Na2SO4, filtered, and solvent was evaporated under reduced pressure to give the crude bromo ketone. The crude product was purified by column chromatography using silica gel (60-120), eluting with EtOAc-PE (1:99).

17

Spectroscopic Data for Selected α-Bromo Ketones
2-Bromocyclohexanone (Entry 2) Liquid.¹³a IR (neat): νmax = 1731, 740, 680 cm-¹. ¹H NMR (60 MHz, CDCl3): δ = 1.25-2.51 (m, 8 H), 3.82-4.13 (dd, J = 1.92 Hz, 1 H).
2-Bromocyclooctanone (Entry 3) Liquid.¹³b IR (neat): νmax = 1730, 685 cm-¹. ¹H NMR (60 MHz, CDCl3): δ = 1.25-1.59 (m, 8 H), 2.17-2.52 (m, 4 H), 4.08-4.17 (t, J = 2.9 Hz, 1 H).
1-Bromoocta-2-one (Entry 4)
Liquid.¹4a IR (neat): νmax = 1730, 686 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 0.91-1.10 (t, J = 9.6 Hz, 3 H), 2.26-2.00 (m, 10 H), 3.74 (s, 2 H).
1-Bromo-3,3-dimethylbutan-2-one (Entry 6)
Liquid.¹4b IR (neat): νmax = 1730, 690 cm-¹. ¹H NMR (300 MHz, CDCl3) δ = 1.14 (s, 9 H), 3.69 (s, 2 H).
1-Bromo-3-phenoxypropan-2-one (Entry 8) Liquid.¹5a IR (neat): νmax = 1737, 668 cm-¹. ¹H NMR (60 MHz, CDCl3): δ = 4.46 (s, 2 H), 5.10 (s, 2 H), 6.99-7.34 (m, 5 H).
1-Bromo-3-(4-chlorophenoxy)propan-2-one (Entry 9)
Liquid.¹5b IR (neat): νmax = 1738, 668 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 4.46 (s, 2 H), 5.10 (s, 2 H), 7.03 (dd, J = 8.1 Hz, 2 H), 7.38 (dd, J = 6.4 Hz, 2 H).
10-Bromo-11-oxo-10,11-dihydro-5 H -dibenzo[ b , f ]azepine-5-carboxamide (Entry 10)
Solid; mp 89 ˚C.¹5c IR (KBr): νmax = 3377, 3325, 3020, 1726, 1696, 744 cm-¹. ¹H NMR (60 MHz, CDCl3): δ = 6.59 (s, 1 H), 6.99-7.92 (m, 8 H).