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Synlett 2011(6): 869-873  
DOI: 10.1055/s-0030-1259923
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Oxidation Reactions in Segmented and Continuous Flow Chemical Processing Using an N-(tert-Butyl)phenylsulfinimidoyl Chloride Monolith

Heiko Lange, Matthew J. Capener, Alexander X. Jones, Catherine J. Smith, Nikzad Nikbin, Ian R. Baxendale, Steven V. Ley*
Innovative Technology Centre, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK
Fax: +44(1223)336442; e-Mail: svl1000@cam.ac.uk;
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Publication History

Received 1 February 2011
Publication Date:
16 March 2011 (online)

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Abstract

A supported version of N-(tert-butyl)phenylsulfinim­idoyl chloride on a monolithic material is described, which can be incorporated into a flow chemical processing arrangement to oxidise a variety of substrates in both stoichiometric and catalytic processes to yield products in high yields and in high purity after in-line workup.

Key words

oxidation - monolith - flow chemistry - polymer-­supported reagents - catalysis

    References and Notes

  • Recent reviews on flow chemistry and the use of supported reagents in flow chemistry:
  • 1a Baumann M. Baxendale IR. Ley SV. Mol. Diversity  2011, in press; DOI: 10.1007/s11030-010-9282-1
    Google Scholar
  • 1b Webb D. Jamison TF. Chem. Sci.  2010,  1:  675 
    Google Scholar
  • 1c Mak XY. Laurino P. Seeberger PH. Beilstein J. Org. Chem.  2009,  5:  No. 19 
    Google Scholar
  • 1d Kirschning A. Beilstein J. Org. Chem.  2009,  5:  No. 15 
    Google Scholar
  • 1e Baxendale IR. Hayward JJ. Lanners S. Ley SV. Smith CD. Heterogeneous Reactions, In Microreactors in Organic Synthesis and Catalysis   Wirth T. Wiley-VCH; Weinheim: 2008.  Chap. 4.2. p.84 
    Google Scholar
  • 1f Ley SV. Baxendale IR. Chimia  2008,  62:  162 
    Google Scholar
  • 1g Baxendale IR. Hayward JJ. Ley SV. Comb. Chem. High Throughput Screen.  2007,  10:  802 
    Google Scholar
  • 1h Ley SV. Baxendale IA. Bream RN. Jackson PS. Leach AG. Longbottom DA. Nesi M. Scott JS. Storer RI. Taylor SJ. J. Chem. Soc., Perkin Trans. 1  2000,  3815 
    Google Scholar
  • Monolithic materials have been employed in other work:
  • 2a Smith CJ. Smith CD. Nikbin N. Ley SV. Baxendale IR. Org. Biomol. Chem.  2011,  9:  1927 
    Google Scholar
  • 2b Baumann M. Baxendale IR. Kirschning A. Ley SV. Wegner J. Heterocycles  2011,  82:  1297 
    Google Scholar
  • 2c Baumann M. Baxendale IR. Ley SV. Synlett  2010,  749 
    Google Scholar
  • 2d Baumann M. Baxendale IR. Ley SV. Nikbin N. Smith CD. Org. Biomol. Chem.  2008,  6:  1587 
    Google Scholar
  • 2e Nikbin N. Ladlow M. Ley SV. Org. Process Res. Dev.  2007,  11:  458 
    Google Scholar
  • 2f Svec F. Huber CG. Anal. Chem.  2006,  78:  2100 
    Google Scholar
  • 2g Altava B. Burguete MI. García-Verdugo E. Luis SV. Vicent MJ. Green Chem.  2006,  8:  717 
    Google Scholar
  • 2h Kunz U. Schönfeld H. Kirschning A. Solodenko W. J. Chromatogr., A  2003,  1006:  241 
    Google Scholar
  • 2i Solodenko W. Kunz U. Jas G. Kirschning A. Bioorg. Med. Chem. Lett.  2002,  12:  1833 
    Google Scholar
  • 2j Kirschning A. Altwicker C. Dräger G. Harders J. Hoffmann N. Hoffmann U. Schönfeld H. Solodenko W. Kunz U. Angew. Chem. Int. Ed.  2001,  40:  3995 ; Angew. Chem. 2001, 113, 4118;
    Google Scholar
  • 2k Tripp JA. Stein JA. Svec F. Fréchet JMJ. Org. Lett.  2000,  2:  195 
    Google Scholar
  • 2l Peters EC. Svec F. Fréchet JMJ. Adv. Mater.  1999,  11:  1169 
    Google Scholar
  • 2m Viklund C. Svec F. Fréchet JMJ. Irgum K. Chem. Mater.  1996,  8:  744 
    Google Scholar
  • 2n Svec F. Fréchet JMJ. Chem. Mater.  1995,  7:  707 
    Google Scholar
  • 2o Wang QC. Svec F. Fréchet JMJ. Anal. Chem.  1995,  67:  670 
    Google Scholar
  • 2p Svec F. Fréchet JMJ. Anal. Chem.  1992,  64:  820 
    Google Scholar
  • Early heavy-metal-based applications:
  • 3a Gardillo G. Orena M. Sandri S. Tetrahedron Lett.  1976,  17:  3985 
    Google Scholar
  • 3b Griffith WP. Ley SV. Whitcomb GP. White AD. J. Chem. Soc., Chem. Commun.  1981,  1625 
    Google Scholar
  • Polymer-supported TPAP:
  • 4a Hinzen B. Ley SV.
    J. Chem. Soc., Perkin Trans. 1  1997,  1907 
    Google Scholar
  • 4b Ley SV. Bolli MH. Hinzen B. Gervois AG. Hall BJ. J. Chem. Soc., Perkin Trans. 1  1998,  2239 
    Google Scholar
  • 4c Hinzen B. Lenz R. Ley SV. Synthesis  1998,  977 
    Google Scholar
  • 5 Iron oxides mixed with solid oxidants like CrO2 and NiO2: Wegner J. Ceylan S. Friese C. Kirschning A. Eur. J. Org. Chem.  2010,  23:  4372 
    Google Scholar
  • 6 KMnO4-based: Sedelmeier J. Ley SV. Baxendale IR. Baumann M. Org. Lett.  2010,  12:  2618 
    CrossrefGoogle Scholar
  • 7 Polymer-supported IBX: Sorg G. Mengel A. Jung G. Rademann J. Angew. Chem. Int. Ed.  2001,  40:  4395 ; Angew. Chem. 2001, 113, 4532
    CrossrefGoogle Scholar
  • Polymer-supported TEMPO:
  • 8a Bolm C. Fey T. Chem. Commun.  1999,  1795 
    Google Scholar
  • 8b Weik S. Nicholson G. Jung G. Rademann J. Angew. Chem. Int. Ed.  2001,  40:  1436 ; Angew. Chem. 2001, 113, 1489
    Google Scholar
  • Polymer-supported Swern-type oxidation:
  • 9a Liu Y. Vederas JC. J. Org. Chem.  1996,  61:  7856 
    Google Scholar
  • 9b Harris JM. Liu Y. Chai S. Andrews MD. Vederas JC.
    J. Org. Chem.  1998,  63:  2407 
    Google Scholar
  • 10 Mukaiyama T. Matsuo J. Yanagisawa M. Bull. Chem. Soc. Jpn.  2000,  1072 
    Google Scholar
  • 11a Mukaiyama T. Kawana A. Fukuda Y. Matsuo J. Bull. Chem. Soc. Jpn.  2001,  390 
    Google Scholar
  • 11b Matsuo J. Mukaiyama T. Kitagawa H. ARKIVOC  2001,  x:  58 
    Google Scholar
  • 11c Kerr WJ. Pearson CM. Thurston GJ. Org. Biomol. Chem.  2006,  4:  47 
    Google Scholar
  • 12a Matsuo J. Iida D. Yamanaka H. Mukaiyama T. Chem. Lett.  2002,  182 
    Google Scholar
  • 12b Matsuo J. Iida D. Yamanaka H. Mukaiyama T. Tetrahedron  2003,  59:  6739 
    Google Scholar
  • For a supported version of N-(tert-butyl)phenyl-sulfinimidoyl chloride in bead form:
  • 13a Matsuo J. Kawana A. Pudhom K. Mukaiyama T. Chem. Lett.  2002,  250 
    Google Scholar
  • 13b Matsuo J. Kawana A. Yanamaka H. Kamiyama H. Bull. Chem. Soc. Jpn.  2003,  76:  1433 
    Google Scholar
  • 14 Prepared according to: Roberts TJ. Rittberg BR. Kovacic P. J. Org. Chem.  1981,  46:  4111 
    CrossrefGoogle Scholar
  • 15 Al-Hourani BJ. Bravo-Vasquez JP. High LRH. Fenniri H. Tetrahedron  2007,  48:  9144 
    CrossrefGoogle Scholar
  • 19 For a reliable procedure to ‘dry’ flow chemistry reactor arrangements, see: Carter CF. Lange H. Sakai D. Baxendale IR. Ley SV. Chem. Eur. J.  2011,  17:  3398 
    CrossrefPubMedGoogle Scholar
16

In cases where the correlation is not strictly linear, the monolith is likely to be of poor quality and should be discarded (see Supporting Information for details).

17

The Vapourtec R2+ and R4 units are available from Vapourtec Ltd, Park Farm Business Centre, Fornham St Genevieve, Bury St Edmunds, Suffolk, IP28 6TS, UK. Website: www.vapourtec.co.uk. See: Baumann, M.; Baxendale, I. R.; Ley, S.V.; Smith, S. D.; Tranmer, G. K. Org. Lett. 2006, 8, 5231.

18

The FlowSyn unit is available from Uniqsis Ltd., 29 Station Road, Shepreth, Cambridgeshire, SG8 6GB, UK. Website: www.uniqsis.com. See the following publication for the use of this platform as a scale-up facility: Palmieri, A.; Ley, S. V.; Hammond, K.; Polyzos, A.; Baxendale, I. R. Tetrahedron Lett. 2009, 50, 3287.