10064
1996, 37, 2813–2816. (e) Zhang, X.; Mashima, K.; Koyano, K.; Sayo, N.; Kumobayashi, H.; Akutagawa, S.;
Takaya, H. J. Chem. Soc., Perkin Trans. 1994, 2309–2322.
5. Liu, G.-B.; Tsukinoki, T.; Kanda, T.; Mitoma, Y.; Tashiro, M. Tetrahedron Lett. 1998, 39, 5991–5994.
6. (a) Adkins, H.; Krsek, G. J. Am. Chem. Soc. 1948, 70, 412–414. (b) Adkins, H.; Billica, H. R. J. Am. Chem. Soc.
1948, 70, 695–698. (c) Rylander, P. Catalytic Hydrogenation in Organic Synthesis; Academic: London, 1979; Vol.
1, pp. 200–202.
7. For examples, see: (a) Carreira, E. M.; Singer, R. A.; Lee, W. J. Am. Chem. Soc. 1994, 116, 8837–8838. (b)
Carreira, E. M.; Lee, W.; Singer, R. A. J. Am. Chem. Soc. 1995, 117, 3649–3650. (c) Singer, R. A.; Carreira, E.
M. J. Am. Chem. Soc. 1995, 117, 12360–12361. (d) Hu, X.; Chen, H.; Zhang, X. Angew. Chem., Int. Ed. Engl.
1999, 38, 3518. (e) Vyskocil, S.; Jaracz, S.; Smrcina, M.; Sticha, M.; Hanus, V.; Polasek, M.; Kocovsky, P. J. Org.
Chem. 1998, 63, 7727–7737; (f) Vyskocil, S.; Smrcina, M.; Hanus, V.; Polasek, M.; Kocovsky, P. J. Org. Chem.
1998, 63, 7738–7748.
8. For the preparation of racemic NOBIN and its optical resolution, see: (a) Ding, K.; Xu, Q.; Wang, Y.; Liu, J.;
Yu, Z.; Du, B.; Wu, Y.; Koshima, H.; Matsuura, T. Chem. Commun. 1997, 693–694. (b) Ding, K.; Wang, Y.;
Yun, H.; Liu, J.; Wu, Y.; Terada, M.; Okubo, Y.; Mikami, K. Chem. Eur. J. 1999, 5, 1734–1737. (c) Smrcina,
M.; Lorenc, M.; Hanus, V.; Sedmera, P.; Kocovsky, P. J. Org. Chem. 1992, 57, 1917–1920. (d) Smrcina, M.;
Vyskocil, S.; Polivkova, J.; Polakova, J.; Kocovsky, P. Collect. Czech. Chem. Commun. 1996, 61, 1520–1524. For
transformation from enantiopure 1 to 3, see: (e) Singer, R. A.; Buchwald, S. L. Tetrahedron Lett. 1999, 40,
1095–1098.
9. A typical procedure for reduction of reduction of 3 to 6: A 500 mL flask was charged with Raney Ni–Al alloy
(2.5 g), water (200 mL) and (R)-NOBIN (356 mg, 1.25 mmol) in isopropanol (30 mL), to which aqueous NaOH
solution (1%, 200 mL) was gradually added over 1 h under stirring at 90°C. The reaction process was monitored
by TLC. After stirring for 7 h at 90°C, the reaction mixture was cooled to room temperature. The insoluble
materials were filtered off with Celite and the solids washed with ethyl acetate. The filtrate was neutralized with
2N HCl to pHꢀ7 and then exacted with ethyl acetate and dried over MgSO4. After the removal of the solvent,
the residue was submitted to column-chromatographic separation on silica gel with petroleum ether/ethyl acetate
(5/1) as eluent to give (R)-6 (275 mg, 75% yield) as a white solid with >99% ee (determined by HPLC on a
Chiralcel OJ column with 93:7 hexane/isopropanol as eluent, 0.7 mL min−1, tR: 10.57 min; tS: 13.94 min). Mp
156–158°C; [h]D20: 103.6 (c=1.0, THF); 1H NMR (300 MHz, CDCl3) l 7.02 (d, 1H, J=8.2 Hz), 6.96 (d, 1H,
J=8.2 Hz), 6.81 (d, 1H, J=8.4 Hz), 6.65 (d, 1H, J=8.3 Hz), 4.60 (br, 1H), 3.35 (br, 2H), 2.77–2.70 (m, 4H),
2.38–2.11 (m, 4H), 1.78–1.64 (m, 8H); 13C NMR (100.6 MHz, CDCl3) l 150.6, 142.5, 137.1, 136.5, 130.4, 129.9,
129.7, 127.9, 122.1, 118.3, 113.3, 112.6, 29.3, 29.2, 27.2, 26.9, 23.3, 23.2, 23.1, 23.0; FT-IR (KBr pellet): 3406,
2934, 2861, 1615, 1482, 1457, 1285, 815 cm−1; EIMS (m/z): 293 (M+, 100%). Anal. calcd for C20H23NO: C, 81.87;
H, 7.90; N, 4.77. Found: C, 81.81; H, 7.96; N, 4.61.
10. Wang, Y.; Guo, H.; Ding, K. Tetrahedron: Asymmetry 2000, 11, in press.
.
.