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Synlett 2004(5): 0901-0903  
DOI: 10.1055/s-2004-820031
LETTER
© Georg Thieme Verlag Stuttgart · New York

Iodine-mediated Ring Closing Alkene Iodoamination with N-Debenzylation for the Asymmetric Synthesis of Polyhydroxylated Pyrrolidines

Stephen G. Davies*, Rebecca L. Nicholson, Paul D. Price, Paul. M. Roberts, Andrew D. Smith
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK
e-Mail: steve.davies@chemistry.oxford.ac.uk;
Further Information

Publication History

Received 4 February 2004
Publication Date:
04 March 2004 (online)

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Abstract

An iodine-mediated ring closing alkene iodoamination with N-debenzylation protocol provides a direct route for the asymmetric synthesis of polyhydroxylated pyrrolidines from homochiral β-amino acid derivatives.

Key words

conjugate addition - iodoamination - debenzylation - ­cyclisation - pyrrolidine

    References

  • 1 Fleet GWJ. Karpas A. Dwek RA. Fellows LE. Tyms AS. Petursson S. Namgoong SK. Ramsden NG. Smith PW. Son JC. Wilson FX. Witty DR. Jacob GS. Rademacher TW. FEBS Lett.  1998,  237:  128 
    CrossrefGoogle Scholar
  • 2 For instance see: Asano N. Nash RJ. Molyneux RJ. Fleet GWJ. Long DD. Frederiksen SM. Marquess DG. Lane AL. Watkin DJ. Winkler DA. Tetrahedron: Asymmetry  2000,  11:  1645 
    CrossrefGoogle Scholar
  • 3 Davis BG. Maughan MAT. Chapman TM. Villard R. Courtney S. Org Lett.  2002,  4:  1026 
    Google Scholar
  • For examples see:
  • 4a Hulme AN. Montgomery CH. Henderson DK. J. Chem. Soc., Perkin Trans. 1  2000,  1837 
    CrossrefGoogle Scholar
  • 4b Verma SK. Nieves Atanes M. Hector Busto J. Thai DL. Rapoport H. J. Org. Chem.  2002,  67:  1314 
    CrossrefGoogle Scholar
  • For instance see:
  • 5a Davies SG. Ichihara O. Tetrahedron: Asymmetry  1991,  2:  183 
    CrossrefGoogle Scholar
  • 5b Bunnage ME. Chippendale AM. Davies SG. Parkin RM. Smith AD. Withey JM. Org. Biomol. Chem.  2003,  3698 
    CrossrefGoogle Scholar
  • For a related approach to proline derivatives by iodine promoted cyclisations see:
  • 6a Jones AD. Knight DW. Hibbs DE. J. Chem. Soc., Perkin Trans. 1.  2001,  1182 
    CrossrefGoogle Scholar
  • 6b Knight DW. Redfern AL. Gilmore J. J. Chem. Soc., Perkin Trans. 1.  2001,  2874 
    CrossrefGoogle Scholar
  • 7a Readily prepared on a multigram scale from d-ribose; (2R,3R)-2,3-O-isopropylidene pent-4-enal was prepared following the procedure developed by: Paquette LA. Bailey S. J. Org. Chem.  1995,  60:  7849 
    CrossrefGoogle Scholar
  • 7b Subsequent olefination of the aldehyde under Masamune-Roush conditions gave compound 1: Blanchette MA. Choy W. Davis JT. Essenfeld AP. Masamune S. Roush WR. Sakai T. Tetrahedron Lett.  1984,  25:  2183 
    CrossrefGoogle Scholar
  • 8 As shown by 1H NMR spectroscopic analysis of the crude reaction mixture the configuration at C(3) within (3S,4S,5R)-2 was assigned by analogy to the model developed previously to explain the stereoselectivity observed during addition of lithium (R)-N-benzyl-N-a-methylbenzylamide to a,b-unsaturated acceptors, see: Costello JF. Davies SG. Ichihara O. Tetrahedron: Asymmetry  1994,  5:  3919 
    Google Scholar
  • 9 Kahara T. Hashimoto Y. Saigo K. Tetrahedron  1999,  55:  6453 
    CrossrefGoogle Scholar
  • 10a Bull SD. Davies SG. Fenton G. Mulvaney AW. Prasad RS. Smith AD. Chem. Commun.  2000,  337 
    CrossrefGoogle Scholar
  • 10b Bull SD. Davies SG. Fenton G. Mulvaney AW. Prasad RS. Smith AD. J. Chem. Soc., Perkin Trans. 1  2000,  3765 
    CrossrefGoogle Scholar
  • 11 Davies SG. Ichihara O. Tetrahedron Lett.  1998,  39:  6045 
    CrossrefGoogle Scholar
  • 12 For the iodine promoted cyclisation and N-debenzylation of an N-benzyl lactam, rather than an potentially oxidisable tertiary amine, see: Edstrom ED. Tetrahedron Lett.  1991,  32:  5709 
    CrossrefGoogle Scholar
  • 13 For an alternative iodoamination approach without debenzylation to piperidines see: Zhi-cai S. Chun-min Z. Guo-qiang L. Heterocycles  1995,  41:  277 
    Google Scholar
  • For example see:
  • 14a Fuson RC. Zirkle CL. J. Am. Chem. Soc.  1948,  70:  2760 
    CrossrefPubMedGoogle Scholar
  • 14b Moragues J. Prieto J. Spickett RGW. Vega A. J. Chem. Soc., Perkin Trans. 1  1976,  938 
    CrossrefPubMedGoogle Scholar
  • 14c Cossy J. Dumas C. Gomez Pardo D. Eur. J. Org. Chem.  1999,  63:  1693 
    CrossrefPubMedGoogle Scholar
  • 14d For recent studies in a related system see: Verhelst SHL. Martinez BP. Timmer MSM. Lodder G. van der Marel GA. Overkleeft HS. van Boom JH. J. Org. Chem.  2003,  68:  9598 
    CrossrefPubMedGoogle Scholar
  • 15a Weber K. Kuklinski S. Gmeiner P. Org. Lett.  2000,  2:  647 
    CrossrefGoogle Scholar
  • 15b Nagle AS. Salvatore RN. Chong B.-D. Jung KW. Tetrahedron Lett.  2000,  41:  3011 
    CrossrefGoogle Scholar
  • 15c Graham MA. Wadsworth AH. Thornton-Pett M. Rayner CM. Chem. Commun.  2001,  966 
    CrossrefGoogle Scholar
  • 16 Abbaspour Tehrani K. Van Syngel K. Boelens M. Contreras J. De Kimpe N. Knight DW. Tetrahedron Lett.  2000,  41:  2507 
    CrossrefGoogle Scholar
  • 17a O’Brien P. Towers TD. J. Org. Chem.  2002,  67:  304 
    CrossrefGoogle Scholar
  • 17b Richardson PF. Nelson LTJ. Sharpless KB. Tetrahedron Lett.  1995,  36:  9241 
    CrossrefGoogle Scholar
  • 17c Liu Q. Marchington AP. Boden N. Rayner CM. J. Chem. Soc., Perkin Trans. 1  1997,  511 
    CrossrefGoogle Scholar
  • 17d de Sousa SE. O’Brien P. Poumellec P. J. Chem. Soc., Perkin Trans. 1  1998,  1483 
    CrossrefGoogle Scholar
18

The crystal structure of the hemi-hydrate of 12 was solved; crystal data for 12, C14H25NO5·0.5 (H2O), colourless plate, M = 296.36, monoclinic, space group C121, a = 23.8038 (15) Å, b = 5.9100 (5) Å, c = 12.0009 (9) Å, U = 1654.3 (2) Å3, Z = 4, µ = 0.091, crystal dimensions 0.05 × 0.1 × 0.5 mm. A total of 2081 unique reflections were measured for 5<θ<30 and 1705 reflections were used in the refinement. The final parameters were wR2 = 0.053 and R1 = 0.045 [I>3σ(I)]. Crystallographic data (excluding structure factors) has been deposited with the Cambridge Crystallographic Data Centre (CCDC 225944).