Angewandte
Chemie
Keywords: alkaloids · asymmetric synthesis · Michael addition ·
.
natural products · total synthesis
[1] a) O. Hoshino in The Alkaloids, Vol. 51 (Ed.: G. A. Cordell),
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Reagents and conditions: a) 1. L-selectride (2.0 equiv), THF,
À788C, 1 day, 92%; 2. NaOH (10%), room temperature,
7.5 days, 83%; 3. NaBH4 (4.0 equiv), MeOH, room temperature,
4 h; 4. (Boc)2O (3.0 equiv), THF, room temperature, 2h, 58%
(2steps).
[3] W.-C. Shieh, J. A. Carlson, J. Org. Chem. 1994, 59, 5463 – 5465.
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Res. Dev. 1999, 3, 425 – 431.
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[6] a) D. H. R. Barton, G. W. Kirby, Proc. Chem. Soc. London 1960,
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Ernst, K. Kieslich, W.-R. Abraham, W. S. Sheldrick, Tetrahedron
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[7] a) B. M. Trost, F. D. Toste, J. Am. Chem. Soc. 2000, 122, 11262 –
11263; b) B. M. Trost, W. Tang, Angew. Chem. 2002, 114, 2919 –
2921; Angew. Chem. Int. Ed. 2002, 41, 2795 – 2797; for a synthesis
of (Æ )-galanthamine, see: c) C. Guillou, J.-L. Beunard, E. Gras,
C. Thal, Angew. Chem. 2001, 113, 4881 – 4882; Angew. Chem. Int.
Ed. 2001, 40, 4745 – 4746; for a synthesis of the galanthamine
ring system, see: d) P. J. Parsons, M. D. Charles, D. M. Harvey,
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Tetrahedron Lett. 2001, 42, 2209 – 2211; e) C. Pilger, B. West-
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synthesis of (Æ )-lycoramine by the Heck reaction, see: f) E.
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[8] M. Node, S. Kodama, Y. Hamashima, T. Baba, N. Hamamichi, K.
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[9] Calculations were performed with the Spartan (version 5.0)
program of Wavefunction Inc. on
computer system.
a
Silicon Graphics O2
[10] In the NOESY spectra of 6a and 6b a correlation was observed
between the methine H atom at C5 and the ortho H atoms of the
pyrogallol moiety at C2of the imidazolidinone; see also: R.
Naef, D. Seebach, Helv. Chim. Acta 1985, 68, 135 – 143.
[11] S. Cacchi, P. G. Ciattini, E. Morera, G. Ortar, Tetrahedron Lett.
1986, 27, 5541 – 5544.
[12] a) [ a]D = À131.4 (c = 0.6, EtOH): S. Y. Han, J. E. Sweeney, E. S.
Bachman, E. J. Schweiger, G. Forloni, J. T. Coyle, B. M. Davis,
M. M. Joullie, Eur. J. Med. Chem. 1992, 27, 673 – 687; b) [a]D =
À112.8 (88% ee, c = 0.5, EtOH);[7a] c) [a]D = À123.1 (96% ee,
c = 0.4, EtOH).[7b]
[13] The optical purity of 12, derived from 9 [Eq (1)], was measured
by HPLC on a chiral stationary phase (Daicel CHIRALCEL
OD, iPrOH/hexane (9:1), 1.0 mLminÀ1); (À)-12: Rt = 50.2min,
(+)-12: Rt = 74.0 min.
Angew. Chem. Int. Ed. 2004, 43, 2659 –2661
ꢀ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2661