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Synthesis 2012(6): 946-952  
DOI: 10.1055/s-0031-1289721
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Copper(I)-Mediated 1,2-Metallate Rearrangements of 1-Metallated Glycals

Krzysztof Jarowicki, Philip Kocieński*, Zofia Komsta, Anna Wojtasiewicz
Institute of Process Research & Development, School of Chemistry, Leeds University, Leeds LS2 9JT, UK
e-Mail: p.j.kocienski@leeds.ac.uk;
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Publication History

Received 2 December 2011
Publication Date:
24 February 2012 (online)

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Abstract

1,2-Metallate rearrangements involving reaction of 1-metallated glycals with organolithium reagents under copper(I) mediation give alkenylpolyol chains in 45-91% yield (19 examples). The reaction was applied to a formal synthesis of KRN7000 as well as a synthesis of a Δ5,6-ceramide derivative.

Key words

1,2-metallate rearrangement - retro-[1,4]-Brook rearrangement - 1-metallated glycals - cuprates - organolithiums - KRN7000

    Primary data for this article are available online and can be cited using the following DOI: 10.4125/pd0025th:
  • Primary Data

    References

  • 1 Kocieński P. Wadman S. Cooper K. J. Am. Chem. Soc.  1989,  111:  2363 
    Google Scholar
  • 2 Fujisawa T. Kurita Y. Kawashima M. Sato T. Chem. Lett.  1982,  1642 
    Google Scholar
  • 3 Kocieński PJ. Barber C. Pure Appl. Chem.  1990,  62:  1933 
    Google Scholar
  • 4 Kocieński P. In Organic Synthesis via Organometallics   Enders D. Gais H.-J. Keim W. Verlag Vieweg; Wiesbaden: 1993.  p.203 
    Google Scholar
  • 5 Jarowicki K. Kocieński PJ. Qun L. Org. Synth. Coll. Vol. 10   Wiley; New York: 2004.  p.662 
    Google Scholar
  • 6 Jarowicki K. Kocieński P. Norris S. O’Shea M. Stocks M. Synthesis  1995,  195 
    Google Scholar
  • 7 Pommier A. Stepanenko V. Jarowicki K. Kocieński PJ. J. Org. Chem.  2003,  68:  4008 
    Google Scholar
  • 8 Fargeas V. Ménez PL. Berque I. Ardisson J. Pancrazi A. Tetrahedron  1996,  52:  6613 
    Google Scholar
  • 9 Ashworth P. Broadbelt B. Jankowski P. Kocieński P. Pimm A. Bell R. Synthesis  1995,  199 
    Google Scholar
  • 10 Hareau-Vittini G. Kocieński P. Reid G. Synthesis  1995,  1007 
    Google Scholar
  • 11 Hareau-Vittini G. Kocieński P. Synlett  1995,  893 
    Google Scholar
  • 12 Milne JE. Jarowicki K. Kocieński PJ. Alonso J. Chem. Commun.  2002,  426 
    Google Scholar
  • 13 Lesimple P. Beau J.-M. Sinaÿ P. J. Chem. Soc., Chem. Commun.  1985,  894 
    Google Scholar
  • 14 Gunn A. Jarowicki K. Kocieński P. Lockhart S. Synthesis  2001,  331 
    Google Scholar
  • 15 Braun M. Mahler H. Justus Liebigs Ann.  1995,  29 
    Google Scholar
  • 16 Bures E. Spinazzé PG. Beese G. Hunt IR. Rogers C. Keay BA. J. Org. Chem.  1997,  62:  8741 
    Google Scholar
  • 17 Comanita BM. Woo S. Fallis AG. Tetrahedron Lett.  1999,  40:  5283 
    Google Scholar
  • 18 Simpkins SME. Kariuki BM. Aricó CS. Cox LR. Org. Lett.  2003,  5:  3971 
    Google Scholar
  • 19 Yamago S. Fujita K. Miyoshi M. Kotani M. Yoshida J. Org. Lett.  2005,  7:  909 
    Google Scholar
  • 20 Mori H. Matsuo T. Yoshioka Y. Katsumura S. J. Org. Chem.  2006,  71:  9004 
    Google Scholar
  • 23 Jarowicki K. Kilner C. Kocieński PJ. Komsta Z. Milne JE. Wojtasiewicz A. Coombs V. Synthesis  2008,  2747 
    Google Scholar
  • 24 Zhang H.-C. Brakta M. Daves GD. Tetrahedron Lett.  1993,  34:  1571 
    Google Scholar
  • 25 Natori T. Koezuka Y. Higa T. Tetrahedron Lett.  1993,  34:  5591 
    Google Scholar
  • 26 Natori T. Morita M. Akimoto K. Koezuka Y. Tetrahedron  1994,  50:  2771 
    Google Scholar
  • 27 Banchet-Cadeddu A. Hénon E. Dauchez M. Renault J.-H. Monneaux F. Haudrechy A. Org. Biomol. Chem.  2011,  9:  3080 
    Google Scholar
  • 28 Chen G. Chien M. Tsuji M. Franck RW. ChemBioChem  2006,  7:  1017 
    Google Scholar
  • 29 Franck RW. Tsuji M. Acc. Chem. Res.  2006,  39:  692 
    Google Scholar
  • 30 Morita M. Motoki K. Akimoto K. Natori T. Sakai T. Sawa E. Yamaji K. Koezuka Y. Kobayashi E. Fukushima H. J. Med. Chem.  1995,  38:  2176 
    Google Scholar
  • 31 Enders D. Terteryan V. Paleček J. Synthesis  2010,  2979 
    Google Scholar
  • 32 Meek SJ. O’Brien RV. Llaveria J. Schrock RR. Hoveyda AH. Nature  2011,  471:  461 
    Google Scholar
  • 33 Figueroa-Pérez S. Schmidt RR. Carbohydr. Res.  2000,  328:  95 
    Google Scholar
  • 36 Black FJ. Kocieński PJ. Org. Biomol. Chem.  2010,  8:  1188 
    Google Scholar
21

In all of our earlier studies we routinely used Me2S as a cosolvent on the assumption that it stabilised the higher order cuprate intermediates. However, we later discovered that Me2S is deleterious to the CuCN-mediated reactions in some cases. In the case of CuBr-mediated reactions, the presence of Me2S as a co-solvent generally had a neutral or beneficial effect.

22

A further advantage to procedure 1 is that CuCN is stable in its Cu(I) oxidation state and hence requires no further purification whereas CuBr should be purified as its Me2S complex since Cu(II) contamination can cause messy reactions and low yields.

34

During their pioneering studies on the synthesis of agelasphin analogues that led to the discovery of KRN7000, Koezuka and co-workers had prepared Δ5,6-sphinganine precursors (see ref. 30).

35

By contrast 1,2-metallate rearrangements of simple lithiated dihydrofurans and dihydropyrans mediated by CuCN require only 1.1-1.5 equivalents of the organolithium reagent or 2.2 equivalents if the corresponding stannane is used.