Download PDF
Synthesis 2010(17): 2922-2925  
DOI: 10.1055/s-0030-1258192
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Metal-Free Synthesis of N-Cyano-Substituted Sulfilimines and Sulfoximines

Ankur Pandey, Carsten Bolm*
Institut für Organische Chemie, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
Fax: +49(241)8092391; e-Mail: Carsten.Bolm@rwth-aachen.de;
Further Information

Publication History

Received 8 July 2010
Publication Date:
04 August 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

Starting from the corresponding sulfides, N-cyano sulfoximines can easily be accessed under metal-free conditions via the corresponding N-cyano-substituted sulfilimines. The reaction sequence involves a sulfide imination with cyanogen amide in presence of a base and N-bromosuccinimide (NBS) followed by an m-chloroperoxybenzoic acid (MCPBA) mediated oxidation of the resulting sulfilimine intermediates.

Key words

halides - metal-free - nitriles - sulfides - sulfilimines - sulfoximines

    References

  • For selected recent examples, see:
  • 1a Walker DP. Zawistoski MP. McGlynn MA. Li J.-C. Kung DW. Bonnette PC. Baumann A. Buckbinder L. Houser JA. Boer J. Mistry A. Han S. Xing L. Guzman-Perez A. Bioorg. Med. Chem. Lett.  2009,  19:  3253 
    Search in Google Scholar
  • 1b García Mancheño O. Dallimore J. Plant A. Bolm C. Adv. Synth. Catal.  2010,  352:  309 
    Search in Google Scholar
  • 1c Jeschke P, Thielert W, and Hungenberg H. inventors; WO 022897  A2.  (Bayer CropScience AG)
  • 1d Jautelat R, Lücking U, Siemeister G, Schulze J, and Lienau P. inventors; (Bayer Schering Pharma AG) 046035  A1. 
  • For reviews, see:
  • 2a Reggelin M. Zur C. Synthesis  2000,  1 
  • 2b Harmata M. Chemtracts  2003,  16:  660 
    Search in Google Scholar
  • 2c Okamura H. Bolm C. Chem. Lett.  2004,  33:  482 
    Search in Google Scholar
  • 2d Bentley R. Chem. Soc. Rev.  2005,  34:  609 
    Search in Google Scholar
  • 2e Worch C. Mayer AC. Bolm C. In Organosulfur Chemistry in Asymmetric Synthesis   Toru T. Bolm C. Wiley-VCH; Weinheim: 2008.  p.209 
  • For recent applications of sulfoximines as chiral ligands in metal catalysis, see:
  • 3a Frings M. Atodiresei I. Wang Y. Runsink J. Raabe G. Bolm C. Chem. Eur. J.  2010,  16:  4577 
    Search in Google Scholar
  • 3b Frings M. Goedert D. Bolm C. Chem. Commun.  2010, DOI: 10.1039/C0CC00996B; and references therein
  • For Cu catalysis, see:
  • 4a Kwart H. Kahn AA. J. Am. Chem. Soc.  1967,  89:  1950 
    Search in Google Scholar
  • 4b Müller JFK. Vogt P. Tetrahedron Lett.  1998,  39:  4805 
    Search in Google Scholar
  • 4c Lacôte E. Amatore M. Fensterbank L. Malacria M. Synlett  2002,  116 
  • For Rh catalysis, see:
  • 4d Okamura H. Bolm C. Org. Lett.  2004,  6:  1305 
    Search in Google Scholar
  • For Ag catalysis, see:
  • 4e Cho GY. Bolm C. Org. Lett.  2005,  7:  4983 
    Search in Google Scholar
  • For Fe catalysis, see:
  • 4f Bach T. Körber C. Tetrahedron Lett.  1998,  39:  5015 
    Search in Google Scholar
  • 4g Bach T. Körber C. Eur. J. Org. Chem.  1999,  64:  1033 
    Search in Google Scholar
  • 4h García Mancheño O. Bolm C. Org. Lett.  2006,  8:  2349 
    Search in Google Scholar
  • 4i Bolm C. García Mancheño O. Chem. Eur. J.  2007,  13:  6674 
    Search in Google Scholar
  • 4j Bolm C. García Mancheño O. Dallimore J. Plant A. Org. Lett.  2009,  11:  2429 
    Search in Google Scholar
  • For metal-free sulfur iminations, see:
  • 5a Cho GY. Bolm C. Tetrahedron Lett.  2005,  46:  8007 
    Search in Google Scholar
  • 5b Siu T. Picard CJ. Yudin AK. J. Org. Chem.  2005,  70:  932 
    Search in Google Scholar
  • 5c Karabuga S. Kazaz C. Kilic H. Ulukanli S. Celik A. Tetrahedron Lett.  2005,  46:  5225 
    Search in Google Scholar
  • 5d Krasnova LB. Hili RM. Chernoloz OV. Yudin AK. ARKIVOC  2005,  (iv):  26 
    Search in Google Scholar
  • 5e García Mancheño O. Bolm C. Org. Lett.  2007,  9:  2951 
    Search in Google Scholar
  • 5f Ochiai M. Naito M. Miyamoto K. Hayashi S. Nakanishi W. Chem. Eur. J.  2010,  in press, DOI: 10.1002/chem.201000759 
  • 6 García Mancheño O. Bistri O. Bolm C. Org. Lett.  2007,  9:  3809 
    CrossrefSearch in Google Scholar
  • 7a Huang JX, Rogers RB, Orr N, Sparks TC, Gifford JM, Loso MR, Zhu Y, and Meade T. inventors; (Dow AgroSciences) WO 149134  A1. Various N-cyano sulfoximines are of interest as agrochemicals. A prominent example is the sap-feeding insecticide Sulfoxaflor, which is scheduled for launch in 2012 by Dow AgroSciences. For details, see:
  • 7b Schade M, Grimm C, Faerber M, Müller K, and Campbell S. inventors; (Syngenta) WO  040623. For a recent report on pesticidal combinations containing Sulfoxaflor, see:
  • For previous syntheses of sulfilimines and sulfoximines with N-cyano groups, see:
  • 8a Swern D. Ikeda I. Whitfield GF. Tetrahedron Lett.  1972,  2635 
  • 8b Stoss P. Satzinger G. Tetrahedron Lett.  1973,  267 
  • 8c Hutchins MGK. Swern D. Tetrahedron Lett.  1981,  22:  4599 
    Search in Google Scholar
  • 8d Kemp JEG. Ellis D. Closier MD. Tetrahedron Lett.  1979,  3781 
  • 8e Zhu Y, Rogers RB, and Huang JX. inventors; (Dow AgroSciences) US 0228027  A1. 
9

Using I2 instead of NBS under those conditions led to the desired products in lower yields.

10

Attempting to use other oxidants such as KMnO4 for the sulfilimine oxidations led to lower sulfoximine yields.