July 1998
SYNLETT
799
Acknowledgement:
Appl. Chem. 1996, 613. c) Hense, T.; Hoppe, D. Synthesis 1997,
1394.
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
11. The determination of the relative configuration of 7 and 8 was
1
established by H NMR NOE experiments. We gratefully thank
Dr. Klaus Bergander for the measurements at the 600 MHz NMR
spectrometer.
References and Notes:
+
X-ray crystal structure determination.
1.
2.
For reviews concerning lentiginosine, castanospermine,
swainsonine, see: a) Brown Jr., K. S.; Trigo, J. R. The Alkaloids,
Chemistry and Pharmacology 1995, 47, 227. b) Michael, J. P. Nat.
Prod. Rep. 1994, 11, 17; 1994, 11, 639; 1995, 12, 535; 1997, 14,
21; 1997, 14, 619.
a) Elbein, A. D.; Molyneux, R. J. in Alkaloids: Chemical and
Biological Perspectives; Pelletier, S. W. (Ed.); Wiley: New York,
1987; Vol. 5, Chapter 1, pp 1 – 54. b) Papandreou, G.; Tong, M.
K.; Ganem, G. J. Am. Chem. Soc. 1993, 115, 11682. c) Legler, G.;
Korth, A.; Berger, A.; Ekhart, C.; Gradnig, G.; Stütz, A. E.
Carbohydr. Res. 1993, 250, 67. d) Kang, M. S.; Bowlin, T. L.;
Vijay, I. K.; Sunkara, S. P. Carbohydr. Res. 1993, 248, 327.
e) Pastuszak, I.; Molyneux, R. I.; James, L. F.; Elbein, A. D
Biochemistry 1990, 29, 1886.
12. The enantiomeric eccess of the acetate was determined by 300
1
MHz H NMR shift experiment using 11 mol% (+)-Eu(hfc) in
3
CDCl .
3
13. Typical procedure:
To
a
solution of racemic 2-(carbamoyloxy)methyl-N-
cinnamylpiperidine (rac-4, 193 mg, 0.50 mmol) and (−)-sparteine
(3, 94 mg, 0.40 mmol) in diethyl ether (3 mL) a 1.3M sec-
butyllithium solution in hexanes (0.375 mmol) was added at − 78
°C. The solution was stirred for 22 h at this temperature and
subsequently chlorotrimethylsilane (0.13 ml, 1.0 mmol) was
added. The reaction mixture was slowly warmed to rt (5 h), aq.
3.
4.
a) Elbein, A. D. Annu. Rev. Biochem. 1987, 56, 497. b) Sunkara, P.
S.; Bowlin, T. L.; Liu, P. S.; Sjoerdsma, A. Biochem. Biophys. Res.
Commun. 1987, 148, 206. c) Gruters, R. A.; Neefjes, J. J.;
Tersmette, M.; de Goede, R. E. Y.; Tulp, A.; Huisman, H. G.;
Miedema, F.; Ploegh, H. L. Nature 1987, 330, 74. d) Humphries,
M. J.; Matsumoto, K.; White, S. L.; Olden, K. Cancer Res. 1986,
46, 5215. e) Dennis, J. W. Cancer Res. 1986, 46, 5131.
K CO solution (2mL) was added, the layers were separated and
2
3
the aqueous layer was extracted three times with diethyl ether. The
combined organic layers were dried over Na SO and evaporated
2
4
in vacuo. The purification of the remaining crude product by flash
a) Brandi, A.; Cicchi, S.; Cordedo, F. M.; Frignoli, R.; Goti, A.;
Picasso, S.; Vogel, P. J. Org. Chem. 1995, 60, 6806. b) Cordero, F.
M.; Cicchi, S.; Goti, A.; Brandi, A. Tetrahedron Lett. 1994, 35,
949. c) Zhou, W.-S.; Xie, W.-G.; Lu, Z.-H.; Pan, X.-F. Tetrahedron
Lett. 1995, 36, 1291. d) Yoda, H.; Kawaguchi, M.; Takanabe, K.
Synlett 1998, 137. e) Yoda, H.; Nakajiama, T.; Takanabe, K.
Synlett 1997, 911. f) Gmeiner, P.; Junge, D. J. Org. Chem. 1995,
60, 3910. g) Cuny, G. D.; Buchwald, S. L. Synlett 1995, 519.
h) Sato, Y.; Nukui, S.; Sodeoka, M.; Shibasaki, M. Tetrahedron
1994, 50, 371.
chromatography (silica gel, petroleum ether/EtOAc/Et N
3
10:0.5:0.15) yielded 36 mg of 10d (R = 0.50) and 30 mg of 9d (R
f
f
= 0.36) [d.r. (9d:10d) = 45:55, 29 %) as well as 118 mg (61 %) of
remaining 4.
20
10d: R = 0.50 (PE/EtOAc/NEt 10:0.5:0.15). [α]
= + 3.9;
f
3
D
20
1
[α]
= + 51.4 (c = 0.28 in CH Cl ). H NMR (300 MHz,
2 2
365
CDCl ): δ = 0.00 (s, 9H, Si(CH ) ); 1.46, 1.48 (s, 6H), 1.62 (s,
3
3 3
6H, Cby-CH ); 1.40 - 1.64 (m, 5H), 1.79 (m, 1H), 1.90 (m, 2H, H-
3
3
2
5 /6/7/8/8a); 2.39 (dd, 1H, J
3 ); 2.43 (d, 1H, J
= 9.75 Hz, J
= 8.82 Hz, H-
a
2,3a
3a,3b
3
= 10.98 Hz, H-2(1)); 2.69 (m, 2H, H-2/
a
2,2(1)
5.
6.
For cyclocarbolithiation see: Bailey, W. F.; Gavaskar, K. V.
Tetrahedron 1994, 50, 5957.
3 ); 2.85 (m, 1H, H-5 ); 3.78 (s, 2H, Cby-CH ); 4.90 (dd, 1H,
b
b
2
3
3
J
= 6.66 Hz, J = 4.29 Hz, H-1); 7.07 – 7.28 (m, 5H, H-
1,8a
1,2
a) Zhang, D.; Liebeskind, L. S. J. Org. Chem. 1996, 61, 2594.
b) Bailey, W. F.; Jiang, X.-L. J. Org. Chem. 1996, 61, 2596.
c) Lorthois, E.; Marek, I.; Normant, J.-F. J. Org. Chem. 1998, 63,
566. d) Oppolzer, W.; Kuo, D. L.; Hutzinger, M. W.; Léger, R.;
Durand, J.-O.; Leslie, C. Tetrahedron Lett. 1997, 38, 6213.
13
aryl). C NMR (75 MHz, CDCl ): δ = − 1.4 q (Si(CH ) ); 24.1 t,
3
3 3
24.2 t (C-6/7); 25.5, 25.1 q, 25.7, 26.1 q (Cby-CH ); 29.2 t (C-8);
3
41.3 d (C-2(1)); 43.5 d (C-2); 52.9 t (C-5); 58.9 t (C-3); 59.7, 61.1
s (Cby-C(CH ) ); 70.5 d (C-8a); 76.5, 76.2 t (Cby-CH ); 82.4 d
3 2
2
(C-1); 96.0, 95.1 s (Cby-C(CH ) ); 124.7 d, 128.0 d, 128.8 d,
3 2
−1
143.9 s (C-aryl); 152.6, 151.6 s (NC=O). IR (Film): ν [cm ]:
7.
8.
Coldham, I.; Hufton, R.; Snowden, D. J. J. Am. Chem. Soc. 1996,
118, 5322.
3060
-
2780 (s, C-H); 1685 (s, NC=O); 1450, 1365.
C
H N O Si (458.718): Calc.: C 68.08, H 9.23, N 6.11. Found:
26 42
2 3
a) Hoppe, D.; Hense, T. Angew. Chem. 1997, 109, 2376; Angew.
Chem. Int. Ed. Engl. 1997, 36, 2282. b) Beak, P.; Basu, A.;
Gallagher, D. J.; Park, Y. S.; Thayumanavan, S. Acc. Chem. Res.
1996, 29, 552.
C 68.36, H 9.46, N 6.53. 9d: R = 0.36 (PE/EtOAc/NEt
f
3
20
20
10:0.5:0.15). Mp: 89 °C (n-hexane). [α]
= − 24.7, [α]
= −
365
D
1
109.4 (c = 0.32 in CH Cl ). H NMR (300 MHz, CDCl ): δ = −
2
2
3
0.05 (s, 9H, Si(CH ) ); 1.15 - 1.90 (m, 19H, Cby-CH /H-6/7/8/
3 3
3
9.
a) Woltering, M. J.; Fröhlich, R.; Hoppe, D. Angew. Chem. 1997,
109, 1804; Angew. Int. Ed. Engl. 1997, 36, 1764. b) Oestreich, M.;
Fröhlich, R.; Hoppe, D. Tetrahedron Lett. 1998, in press.
3
8a); 2.03 (m, 1H, H-5 ); 2.38 (d, 1H, J = 11.19 Hz, H-2(1));
a
2,9
2.65 (m, 2H, H-2/3 ); 3.01 (m, 2H, H-3 /5 ); 3.72 (s, 2H, H-5');
a
b b
3
3
4.74 (dd, 1H, J
= 7.62 Hz, J = 4.53 Hz, H-1); 7.02 - 7.07
(m, 3H), 7.15 - 7.22 (m, 2H, H-aryl). C NMR (75 MHz, CDCl ):
1,8a
1,2
13
10. a) Haller, J.; Hense, T.; Hoppe, D. Synlett 1993, 726. b) Hoppe,
D.; Hintze, F.; Tebben, P.; Paetow, M.; Ahrens, H.; Schwerdtfeger,
J.; Sommerfeld, P.; Haller, J.; Guarnieri, W.; Kolczewski, S.;
Hense, T.; Hoppe, I. Pure Appl. Chem. 1994, 66, 1479. c) Hoppe,
D.; Ahrens, H.; Guarnieri, W.; Helmke, H.; Kolczewski, S. Pure
3
δ = − 1.1 q (Si(CH ) ); 24.0 t (C-7); 24.8 t (C-6); 25.4 q, 25.6,
3 3
25.9, 27.0 q (Cby-CH ); 28.7 t (C-8); 42.1 d (C-2(1)); 43.0 d (C-
3
2); 53.3 t (C-5); 58.8 t (C-3); 59.3, 60.3 s (Cby-C(CH ) ); 69.0 d
3 2
(C-8a); 76.4, 76.1 t (Cby-CH ); 82.9 d (C-1); 95.7 [94.4] s (Cby-
2