M. Katoh et al. / Tetrahedron Letters 46 (2005) 5161–5163
5163
Schlock, R. R. Tetrahedron 1999, 55, 8141–8153; (g)
Phillips, A. J.; Abell, A. D. Aldrichim. Acta 1999, 32, 75–
ing reductive deamination of a-amino carbonyl
compound with samarium diiodide and RCM as the
key reactions. The methodology described here is
obviously applicable to the stereoselective synthesis of
other Nuphar alkaloids in optically active forms.
90; (h) Furstner, A. Angew. Chem., Int. Ed. Engl. 2000, 39,
¨
3012–3043; (i) Trnka, T. M.; Grubbs, R. H. Acc. Chem.
Res. 2001, 34, 18–29; (j) Hoveyda, A. H.; Schrock, R. R.
Chem. Eur. J. 2001, 7, 945–950; (k) Schrock, R. R.;
Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 4592–
4633.
Acknowledgements
12. Selected data for compound 14: [a]D ꢀ162.3 (c 0.57,
CHCl3). 1H NMR (CDCl3) d 0.93 (3H, d, J = 6.6 Hz),
1.16–1.29 (1H, m), 1.35–1.54 (4H, m), 1.66–2.02 (5H, m),
2.27–2.40 (2H, m), 2.93–3.03 (2H, m), 5.36 (1H, m), 6.48
(1H, dd, J = 0.8, 1.5 Hz), 7.33–7.37 (2H, m); 13C NMR
(CDCl3) d 18.8, 20.7, 31.9, 33.4, 34.4, 37.5, 56.9, 61.2, 64.2,
109.5, 118.3, 128.4, 131.4, 139.3, 142.8; IR (thin film) 1596,
1573, 1501, 1450, 1439, 1377, 1349, 1330, 1308, 1292, 1250,
1219, 1184, 1163, 1125, 1097, 1070, 1033, 1020, 977,
This work was supported in part by a grant from the
Ministry of Education, Culture, Sports, Science and
Technology of Japan.
References and notes
874 cmꢀ1
; HRMS m/z found: 231.1646 (calcd for
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C15H21NO: 231.1623).
13. Selected data for compound 15: [a]D ꢀ104.4 (c 0.16,
CHCl3). 1H NMR (CDCl3) d 1.02 (3H, d, J = 6.1 Hz),
1.35–1.66 (6H, m), 1.67–1.79 (1H, m), 1.88–2.11 (2H, m),
2.18–2.32 (1H, m), 2.48 (1H, ddd, J = 4.7, 8.2, 9.2 Hz),
2.84 (1H, d, J = 16.6 Hz), 2.94 (1H, dt, J = 1.2, 16.6 Hz),
4.03 (1H, t, J = 4.1 Hz), 5.37 (1H, m), 6.37 (1H, m), 7.35
(1H, s), 7.39 (1H, t, J = 1.6 Hz); 13C NMR (CDCl3) d 18.9,
20.7, 27.6, 30.6, 31.2, 36.7, 54.4, 54.7, 56.8, 111.9, 118.0,
124.9, 131.5, 139.9, 142.3; IR (thin film) 1499, 1458, 1439,
1377, 1261, 1188, 1176, 1160, 1130, 1108, 1061, 1045, 1028,
972, 874 cmꢀ1; HRMS m/z found: 231.1643 (calcd for
C15H21NO: 231.1623).
14. Although the enamine was found to be unstable towards
isolation, 1H and 13C NMR spectra were obtained. 1H
NMR data for the enamine: 1H NMR (CDCl3) d 0.98 (3H,
d, J = 6.4 Hz), 1.58 (3H, d, J = 0.8 Hz), 1.69–2.14 (4H, m),
2.19–2.33 (1H, m), 2.52 (1H, ddd, J = 3.8, 9.7, 9.9 Hz),
2.89 (1H, dt, J = 1.2, 16.8 Hz), 3.52 (1H, d, J = 16.8 Hz),
4.78 (1H, dd, J = 2.3, 6.3 Hz), 5.43–5.49 (1H, m), 6.41
(1H, dd, J = 0.8, 1.8 Hz), 7.35 (1H, dd, J = 1.6, 1.8 Hz),
7.39 (1H, s); 13C NMR (CDCl3) d 18.5, 20.6, 30.9, 31.1,
32.7, 53.9, 60.5, 102.3, 110.7, 119.1, 124.8, 132.2, 138.9,
139.5, 142.3.
15. The diastereoselectivity for the hydrogenation of com-
pound 14 was observed to be ca. 4:1 (1:2) by the analysis
of H NMR spectrum of the crude products.
1
16. Kotake, M.; Kawasaki, I.; Matsutani, S.; Kusumoto, S.;
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