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Synlett 2007(12): 1948-1950  
DOI: 10.1055/s-2007-984496
LETTER
© Georg Thieme Verlag Stuttgart · New York

Straightforward Synthesis of Strained α,β-Epoxysulfones via Epoxidation of Vinylsulfones Using N-Methylmorpholine N-Oxide as Epoxidizing Reagent

Rocío Rincón, Ana Aljarilla, María Criado, Joaquín Plumet*
Departamento de Química Orgánica I, Facultad de Química, Universidad Complutense, 28040 Madrid, Spain
e-Mail: plumety@quim.ucm.es;
Further Information

Publication History

Received 19 April 2007
Publication Date:
25 June 2007 (online)

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Abstract

An efficient, stereoselective route to the α,β-epoxy­sulfones using N-methylmorpholine N-oxide (NMO) as epoxidizing reagent is described.

Key words

vinylsulfone - α,β-epoxysulfone - N-methylmorpholine N-oxide - epoxidation

    References and Notes

  • 1a Review: Arjona O. Plumet J. Curr. Org. Chem.  2002,  6:  571 
    Article in Thieme ConnectGoogle Scholar
  • For other comprehensive reviews on the synthetic applications of oxa- and azanorbornene derivatives, see:
  • 1b Vogel P. Cossy J. Plumet J. Arjona O. Tetrahedron  1999,  55:  13521 
    Article in Thieme ConnectGoogle Scholar
  • 1c Vogel P. Curr. Org. Chem.  2000,  65:  455 
    Article in Thieme ConnectGoogle Scholar
  • 1d Arjona O. Csáky AG. Plumet J. Eur. J. Org. Chem.  2002,  611 
    Article in Thieme ConnectGoogle Scholar
  • 1e Medel R. Plumet J. In Targets in Heterocyclic Systems   Vol. 8:  Attanasi OA. Spinelli D. Società Chimica Italiana: 2004.  p.162-186  
    Article in Thieme ConnectGoogle Scholar
  • 1f Ishikura M. Katagiri N. Recent Res. Dev. Org. Chem.  2004,  8:  197 
    Article in Thieme ConnectGoogle Scholar
  • 1g Robina I. Vogel P. Synthesis  2005,  675 
    Article in Thieme ConnectGoogle Scholar
  • 1h Vogel P. In The Organic Chemistry of Sugars   Levy DE. Fugedi P. Taylor and Francis Group/CRC Press; Boca Ratón: 2006.  Chap. 13. p.629-725  
    Article in Thieme ConnectGoogle Scholar
  • 2 Arjona O. de Dios A. de la Pradilla RF. Plumet J. Viso A. J. Org. Chem.  1994,  59:  3906 
    CrossrefGoogle Scholar
  • 3 Arjona O. León ML. Plumet J. Org. Lett.  2000,  2:  3683 
    CrossrefGoogle Scholar
  • 4a Arjona O. Borrallo C. Iradier F. Medel R. Tetrahedron Lett.  1998,  39:  1977 
    CrossrefGoogle Scholar
  • 4b Arjona O. Iradier F. Medel R. Plumet J. Tetrahedron: Asymmetry  1999,  10:  3431 
    CrossrefGoogle Scholar
  • 4c Arjona O. Lorenzo G. Medel R. Plumet J. Tetrahedron Lett.  2001,  42:  7041 
    CrossrefGoogle Scholar
  • 5 Arjona O. Iradier F. Plumet J. Martínez-Alcázar MP. Hernández-Cano F. Fonseca I. Tetrahedron Lett.  1998,  39:  8335 
    CrossrefGoogle Scholar
  • 6 Arjona O. Menchaca R. Plumet J. J. Org. Chem.  2001,  66:  2400 
    CrossrefGoogle Scholar
  • 7 Leung-Toung R. Liu Y. Muchowski JM. Wu YL. J. Org. Chem.  1998,  63:  3235 
    CrossrefGoogle Scholar
  • 8a Simpkins NL. In Sulfones in Organic Synthesis, Tetrahedron Organic Chemistry Series   Pergamon Press; Oxford: 1993. 
    Article in Thieme ConnectGoogle Scholar
  • For some more recent references, see:
  • 8b Diez D. Beneitez MT. Marcos IS. Garrido NM. Basabe P. Sanz F. Broughton HB. Urones JG. Org. Lett.  2003,  5:  4361 
    Article in Thieme ConnectGoogle Scholar
  • 8c Diez D. Beneitez MT. Gil MJ. Moro RF. Marcos IS. Garrido NM. Basabe P. Urones JG. Synthesis  2005,  565 
    Article in Thieme ConnectGoogle Scholar
  • For some synthetically useful transformations of this kind of compound, see:
  • 9a Arjona O. Menchaca R. Plumet J. Tetrahedron  2000,  56:  3901 
    CrossrefGoogle Scholar
  • 9b Hodgson DM. Maxwell CR. Wisedate R. Matthews IR. Carpenter KJ. Dickenson AH. Wonnacott S. J. Chem. Soc., Perkin Trans. 1  2001,  3150 
    CrossrefGoogle Scholar
  • 10a Simpkins NL. In Sulfones in Organic Synthesis, Tetrahedron Organic Chemistry Series   Pergamon Press; Oxford: 1993.  p.55-58  
    CrossrefGoogle Scholar
  • 10b interestingly, epoxidation of sulfone 14 with MCPBA (CH2Cl2, 20 °C, 4 h) provides the exo-epoxide 15 without the formation of Baeyer-Villiger oxidation product (Scheme 3). See: Prakash Rao HS. Murali R. Taticchi A. Scheeren HW. Eur. J. Org. Chem.  2001,  2869 
    CrossrefGoogle Scholar
  • 11 The exo selectivity in the nucleophilic additions and cycloadditions of the bicyclo[2.2.1]heptene double bond is a characteristic behavior of these compounds. For a comprehensive discussion, see: Huisgen R. Pure Appl. Chem.  1981,  53:  171 ; see in particular p. 181 and following
    Google Scholar
  • 12 Four isolated cases regarding the epoxidation reaction of α,β-unsaturated esters 16 with an amine oxide (NMO) to give endo-epoxides 17 (Scheme 4) have been previously described. See: Andres CJ. Spetseris N. Norton JR. Meyers AJ. Tetrahedron Lett.  1995,  36:  1613 
    CrossrefGoogle Scholar
  • Compounds 4 and 5 were synthesized by cycloaddition reaction of p-toluenesulfonylacetylene with furan and N-Boc pyrrole, respectively:
  • 13a Compound 4: Arjona O. Iradier F. Medel R. Plumet J. Heterocycles  1999,  50:  653 
    CrossrefGoogle Scholar
  • 13b Compound 5: Altenbach HJ. Blech B. Marco JA. Vogel E. Angew. Chem., Int. Ed. Engl.  1982,  21:  778 
    CrossrefGoogle Scholar
  • 13c See also: Chen Z. Trudell ML. Tetrahedron Lett.  1994,  35:  9649 
    CrossrefGoogle Scholar
  • 13d

    In the same fashion, cycloaddition of cyclopentadiene and p-toluenesulfonylacetylene gave 6 in 99% isolated yield. Compound 7 (30% isolated yield) was prepared by trapping of isobenzofuran 22 [generated by reaction of 3,6-di(2′-pyridyl)-5-tetrazine(19) with 1,4-dihydro-1,4-endoxynaphthalene (20)] with p-toluene-sulfonylacetylene (Scheme [5] ). Analogous generation and trapping of N-Boc isoindole 23 gave compound 8 (62%). To the best of over knowledge these are the first cases concerning the application of the ‘tetrazine method’ to the synthesis of bicyclic α,β-unsaturated sulfones. Full details of the procedure will be reported in due course or upon request.
    CrossrefGoogle Scholar
  • 13e For the generation of isobenzofuran, see: Warrener RN. J. Am. Chem. Soc.  1971,  93:  2346 
    CrossrefGoogle Scholar
  • 13f For the generation of N-Boc isoindole, see: Priestly GM. Warrener RN. Tetrahedron Lett.  1972,  4295 
    CrossrefGoogle Scholar
14

Typical Experimental Procedure: To a solution of compounds 4-8 (0.43 mmol) in anhyd CH2Cl2 (6 mL), NMO (0.86 mmol) was added in one portion under argon at 0 °C. The mixture was allowed to react at r.t. during 24 h. After this time the solvent was removed under reduced pressure and the residual material was purified by column chromatography (hexane-EtOAc, 4:1).