LETTER
Synthesis of (+)-Hyacinthacine B1
1143
(8) Pyrrolidines: (a) Kanazawa, A.; Gillet, S.; Delair, P.;
In summary, (+)-hyacinthacine B1 has been efficiently
prepared (4.4% overall yield) in enantiopure form through
an asymmetric cycloaddition approach. This approach,
which does not rely on chiral-pool substrates, is highly
flexible and should be useful for the synthesis of yet other
hyacinthacines.
Greene, A. E. J. Org. Chem. 1998, 63, 4660. (b) Delair, P.;
Brot, E.; Kanazawa, A.; Greene, A. E. J. Org. Chem. 1999,
64, 1383. (c) Ceccon, J.; Poisson, J.-F.; Greene, A. E. Synlett
2005, 1413.
(9) Indolizidines: (a) Pourashraf, M.; Delair, P.; Rasmussen, M.;
Greene, A. E. J. Org. Chem. 2000, 65, 6966. (b) Rasmussen,
M.; Delair, P.; Greene, A. E. J. Org. Chem. 2001, 66, 5438.
(c) Ceccon, J.; Poisson, J.-F.; Greene, A. E. Org. Lett. 2006,
8, 4739.
(10) Pyrrolizidines: (a) Roche, C.; Delair, P.; Greene, A. E. Org.
Lett. 2003, 5, 1741. (b) Roche, C.; Kadlecíková, K.; Veyron,
A.; Delair, P.; Philouze, C.; Greene, A. E.; Flot, D.;
Burghammer, M. J. Org. Chem. 2005, 70, 8352.
(11) Kato, A.; Adachi, I.; Miyauchi, M.; Ikeda, K.; Komae, T.;
Kizu, H.; Kameda, Y.; Watson, A. A.; Nash, R. J.; Wormald,
M. R.; Fleet, G. W. J.; Asano, N. Carbohydr. Res. 1999, 316,
95.
Supporting Information for this article is available online at
Acknowledgment
We thank Professor N. Asano for a comparison sample of natural
hyacinthacine B1 and Professor P. Dumy for his interest in our
work. Financial support from the CNRS and the Université Joseph
Fourier is gratefully acknowledged.
(12) To the best of our knowledge, only a very recent synthesis of
hyacinthacine B1 starting from L-pyroglutamic acid has been
published prior to this report. See: Sengoku, T.; Satoh, Y.;
Oshima, M.; Takahashi, M.; Yoda, H. Tetrahedron 2008, 64,
8052.
References and Notes
(1) Iminosugars; Compain, P.; Martin, O. R., Eds.; John Wiley
and Sons: Chichester, 2007.
(13) Both (R)- and (S)-Stericol® are now available from Sigma-
Aldrich. (S)-Stericol® was chosen on the basis of previous
work8–10 that indicated it would lead to natural hyacinthacine
B1.
(2) (a) Asano, N.; Nash, R. J.; Molyneux, R. J.; Fleet, G. W. J.
Tetrahedron: Asymmetry 2000, 11, 1645. (b) Butters, T. D.;
Dwek, R. A.; Platt, F. M. Chem. Rev. 2000, 100, 4683.
(c) Robina, I.; Moreno-Vargas, A. J.; Carmona, A. T.;
Vogel, P. Curr. Drug Metab. 2004, 5, 329. (d) Borges de
Melo, E.; da Silva Gomes, A.; Carvalho, I. Tetrahedron
2006, 62, 10277. (e) Gerber-Lemaire, S.; Juillerat-
Jeanneret, L. Mini Rev. Med. Chem. 2006, 6, 1043.
(3) For a review on polyhydroxylated pyrrolizidines, see:
(a) Yoda, H. Curr. Org. Chem. 2002, 6, 223. For a review
on pyrrolizidines, see: (b) Liddell, J. R. Nat. Prod. Rep.
2002, 19, 773. (c) Liddell, J. R. Nat. Prod. Rep. 2001, 18,
441. (d) Liddell, J. R. Nat. Prod. Rep. 2000, 17, 455.
(e) Liddell, J. R. Nat. Prod. Rep. 1999, 16, 499. (f) Liddell,
J. R. Nat. Prod. Rep. 1998, 15, 363. (g) Nash, R. J.; Watson,
A. A.; Asano, N. In Alkaloids: Chemical & Biological Per-
spectives, Vol. 11; Pelletier, S. W., Ed.; Elsevier Science:
Oxford, 1996, 345.
(14) The lactam was obtained as a 93:7 (1H NMR) mixture of
diastereomers. The minor enantiomer filtered out over the
remainder of the synthesis.
(15) (a) Bruylants, P. Bull. Soc. Chim. Belg. 1924, 33, 467. For
mechanistic studies, see: (b) Beaufort-Droal, V.; Pereira, E.;
Théry, V.; Aitken, D. J. Tetrahedron 2006, 62, 11948.
(c) Aitken, D. J.; Beaufort, V.; Chalard, P.; Cladière, J. L.;
Dufour, M.; Pereira, E.; Théry, V. Tetrahedron 2002, 58,
5933.
(16) For a review, see: (a) Enders, D.; Shilvock, J. P. Chem. Soc.
Rev. 2000, 29, 359. See also: (b) Husson, H. P.; Royer, J.
Chem. Soc. Rev. 1999, 28, 383.
(17) (a) Durand, J.-O.; Larchevêque, M.; Petit, Y. Tetrahedron
Lett. 1998, 39, 5743. (b) Matsubara, R.; Kawai, N.;
Kobayashi, S. Angew. Chem. Int. Ed. 2006, 45, 3814.
(18) (a) Xia, Q.; Ganem, B. Tetrahedron. Lett. 2002, 43, 1597.
(b) White, J. M.; Tunoori, A. R.; Georg, G. I. J. Am. Chem.
Soc. 2000, 122, 11995.
(19) Kim, S.; Ahn, K. H. J. Org. Chem. 1984, 49, 1717.
(20) For a review, see: Jones, G. R.; Landais, Y. Tetrahedron
1996, 52, 7599.
(4) See: Kato, A.; Kato, N.; Adachi, I.; Hollinshead, J.; Fleet,
G. W.; Kuriyama, C.; Ikeda, K.; Asano, N.; Nash, R. J.
J. Nat. Prod. 2007, 70, 993; and references cited therein.
(5) For recent examples, see: (a) Chabaud, L.; Landais, Y.;
Renaud, P. Org. Lett. 2005, 7, 2587. (b) Desvergenes, S.;
Py, S.; Vallée, Y. J. Org. Chem. 2005, 70, 1459.
(c) Donohoe, T. J.; Sintim, H. O.; Hollinshead, J. J. Org.
Chem. 2005, 70, 7297. (d) Dewi-Wülfing, P.; Blechert, S.
Eur. J. Org. Chem. 2006, 1852. (e) Donohoe, T. J.; Thomas,
R. E. Chem. Rec. 2007, 7, 180. (f) Zhou, L.; Chen, J.; Cao,
X.-P. Synthesis 2007, 1359. (g) Izquierdo, I.; Plaza, M. T.;
Tamayo, J. A.; Sanchez-Cantalejo, F. Eur. J. Org. Chem.
2007, 6078. (h) Izquierdo, I.; Plaza, M. T.; Tamayo, J. A.;
Yanez, V.; Lo Re, D.; Sanchez-Cantalejo, F. Tetrahedron
2008, 64, 4613. (i) Donohoe, T. J.; Thomas, R. E.;
Cheeseman, M. D.; Rigby, C. L.; Bhalay, G.; Linney, I. D.
Org. Lett. 2008, 10, 3615. (j) Chandrasekhar, S.; Parida,
B. B.; Rambabu, C. J. Org. Chem. 2008, 73, 7826. (k) For
asymmetric syntheses of related compounds, see: Denmark,
S. E.; Martinborough, E. A. J. Am. Chem. Soc. 1999, 121,
3046 (australine). (l) Trost, B. M.; Aponick, A.; Stanzl, B.
N. Chem. Eur. J. 2007, 13, 9547 (australine). (m)Denmark,
S. E.; Hurd, A. R. J. Org. Chem. 2000, 65, 2875 (casuarine).
(6) Reddy, P. V.; Veyron, A.; Koos, P.; Bayle, A.; Greene,
A. E.; Delair, P. Org. Biomol. Chem. 2008, 6, 1170.
(7) Greene, A. E.; Charbonnier, F. Tetrahedron Lett. 1985, 26,
5525.
(21) See, for example: (a) Smitrovich, J. H.; Woerpel, K. A.
J. Org. Chem. 1996, 61, 6044. (b) Molander, G. A.;
Nichols, P. J. J. Org. Chem. 1996, 61, 6040. (c) Overman,
L. O.; Wild, H. Tetrahedron Lett. 1989, 30, 647.
(d) Polniaszek, R. P.; Dillard, L. W. J. Org. Chem. 1992, 57,
4103. See also ref. 22g
(22) (a) Fleming, I.; Ghosh, S. K. J. Chem. Soc., Chem. Commun.
1992, 1775. (b) Chen, R. M.; Weng, W. W.; Luh, T. Y.
J. Org. Chem. 1995, 60, 3272. (c) Shimada, T.; Mukaide,
K.; Shinohara, A.; Han, J. W.; Hayashi, T. J. Am. Chem. Soc.
2002, 124, 1584. (d) Berry, M. B.; Griffiths, R. J.; Sanganee,
M. J.; Steel, P. G.; Whelligan, D. K. Tetrahedron Lett. 2003,
44, 9135. (e) Landais, Y.; Mahieux, C. Tetrahedron Lett.
2005, 46, 675. (f) Restorp, P.; Fischer, A.; Somfai, P. J. Am.
Chem. Soc. 2006, 128, 12646. (g) Dressel, M.; Restorp, P.;
Somfai, P. Chem. Eur. J. 2008, 14, 3072; and references
cited therein.
(23) The corresponding tetraacetates were also found to be
identical by chromatography (TLC) in several different
solvent systems and by 1H and 13C NMR.
Synlett 2009, No. 7, 1141–1143 © Thieme Stuttgart · New York