Synlett 2011(11): 1533-1536  
DOI: 10.1055/s-0030-1260772
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Weinreb Amide Based Building Blocks for the Synthesis of α- and β-Organylseleno Aryl Ketones

Sivaraman Balasubramaniam, Indrapal Singh Aidhen*
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India
Fax: +91(44)22574202; e-Mail: isingh@iitm.ac.in;
Further Information

Publication History

Received 24 March 2011
Publication Date:
15 June 2011 (online)

Abstract

A new strategy for the synthesis of α- and β-organylseleno aryl ketones has been achieved. The strategy is based on the use of hitherto unreported 2,2′-diselenediylbis(N-methoxy-N-methyl­acetamide) and 3,3′-diselenediylbis(N-methoxy-N-methylpropan­amide). The envisaged synthetic equivalents combine the usefulness of Weinreb amide (WA) functionality and those innate with selenium for the first time. The synthesis of the targets, α- and β-organylseleno aryl ketones could be achieved by the reductive cleavage of Se-Se bond, followed by the alkylation on selenium, and the addition of arylmagnesium halide onto the WA functionality therein.

    References and Notes

  • 1 Freudendahl DM. Shahzad SA. Wirth T. Eur. Org. Chem.  2009,  1649 
  • 2a Braga HC. Stefani HA. Paixao MW. Santos FW. Ludtke DS. Tetrahedron  2010,  66:  3441 
  • 2b Braga HC. Wouters AD. Zerillo FB. Ludtke DS. Carbohydr. Res.  2010,  345:  2328 
  • 3a Victoria FN. Radatz CS. Sachini M. Jacob RG. Perin G. Da Silva WP. Lenardão EJ. Tetrahedron Lett.  2009,  50:  6761 ; and references cited therein
  • 3b Paulmier C. Houllemare D. Ponthieux S. Outurquin F. Synthesis  1997,  101 
  • 3c Cossy J. Furet N. Tetrahedron Lett.  1993,  34:  7755 
  • 3d Magnus P. Rigollier P. Tetrahedron Lett.  1992,  33:  6111 
  • 3e Back T. Kerr R. Tetrahedron Lett.  1982,  23:  3241 
  • 3f Sonoda N. Miyoshi N. Yamamoto T. Kambe N. Murai S. Tetrahedron Lett.  1982,  23:  4813 
  • 4 Bao W. Zhang Y. Synlett  1996,  1187 
  • 5 Nishiyama Y. Kawamatsu H. Funato S. Tokunaga K. Sonoda N. J. Org. Chem.  2003,  68:  3599 
  • 6 Reich HJ. Jasperse CP. Renga JM. J. Org. Chem.  1986,  51:  2981 
  • 7a Meciarova M. Toma S. Lett. Org. Chem.  2006,  3:  794 
  • 7b Chu C.-M. Gao S. Sastry MNV. Kuo C.-W. Lu C. Liu J.-T. Yao C.-F. Tetrahedron  2007,  63:  1863 ; and references cited therein
  • 8a Nahm S. Weinreb SM. Tetrahedron Lett.  1981,  22:  3815 
  • For reviews on Weinreb amide chemistry, see:
  • 8b Sivaraman B. Aidhen IS. Synthesis  2008,  3707 
  • 8c Singh J. Satyamurthi N. Aidhen IS. J. Prakt. Chem.  2000,  342:  340 
  • 8d Mentzel M. Hoffmann HMR.
    J. Prakt. Chem.  1997,  339:  517 
  • 8e Sibi MP. Org. Prep. Proced. Int.  1993,  25:  15 
  • 9a Sivaraman B. Harikrishna K. Aidhen IS. Tetrahedron Lett.  2011,  52:  2683 
  • 9b Sivaraman B. Aidhen IS. Eur. J. Org. Chem.  2010,  4991 
  • 9c Sivaraman B. Senthilmurugan A. Aidhen IS. Synlett  2007,  2841 
  • 9d Sivaraman B. Aidhen IS. Synlett  2007,  959 
  • 10 Logan G. Igunbor C. Chen G.-X. Davis H. Simon A. Salon J. Synlett  2006,  1554 
  • 11 Klayman DL. Griffin TS. J. Am. Chem. Soc.  1973,  95:  197 
  • 12 Ghosh AK. Banerjee S. Sinha S. Kang SB. Zajc B. J. Org. Chem.  2009,  74:  3689 
  • 13 Selvamurugan V. Aidhen IS. Synthesis  2001,  2239 
  • 16 Déziel R. Malenfant E. Thibault C. Fréchette S. Gravel M. Tetrahedron Lett.  1997,  38:  4753 
  • 17 Campbell TW. McCullough JD. J. Am. Chem. Soc.  1945,  67:  1965 
14

2,2′-Diselenediylbis( N -methoxy- N -methylacetamide) (4) Yield 45%. R f = 0.20 (hexanes-EtOAc = 6:4), yellow colored liquid. ¹H NMR (400 MHz, CDCl3): δ = 3.14 (s, 3 H, NCH3), 3.52 (s, 2 H, SeCH2), 3.68 (s, 3 H, OCH3). ¹³C NMR (100 MHz, CDCl3): δ = 29.6, 32.5, 61.5, 171.2. IR (CHCl3): 2929, 2850, 1637, 1445, 1155 cm. ESI-HRMS: m/z calcd for C8H16N2O4NaSe2 [M + Na]+: 386.9338; found: 386.9344.
3,3′-Diselenediylbis( N -methoxy- N -methylpropan-amide) (5)
Yield 65%. R f =0.25 (hexanes-EtOAc = 6:4), yellow colored liquid. ¹H NMR (400 MHz, CDCl3): δ = 2.94-2.98 (m, 2 H, COCH2), 3.12-3.15 (m, 2 H, SeCH2), 3.19 (s, 3 H, NCH3), 3.70 (s, 3 H, OCH3). ¹³C NMR (100 MHz, CDCl3): δ = 22.1, 29.1, 32.4, 61.5, 171.5. IR (CHCl3): 2921, 2847, 1626, 1458, 1166 cm. ESI-HRMS: m/z calcd for C10H21N2O4Se2 [M + H]+: 392.9832; found: 392.9833.

15

The sugar halides 13 and 14 were prepared through multistep reaction sequence from commercially available monosacchride d-(+)-glucono-1,5-lactone.