M. Tiecco et al. / Tetrahedron Letters 48 (2007) 4343–4345
4345
18
11. Selected data for compound 3: mp 59 ꢁC; ½aꢀD ꢁ3.57 (c
1.97 in CHCl3); HPLC analysis: Chiralcel OD-H column
(250 · 4 mm, Daicel), eluent: i-PrOH/hexane (0.5:99.5)
flow rate: 0.5 mL/min, UV detection at 220 nm; tR
29.6 min: er >99:1; 1H NMR (200 MHz, CDCl3, TMS):
14. Derkach, N. Y.; Tishchenko, N. P. Zh. Organ. Khim.
1977, 13, 100–103; Derkach, N. Y.; Tishchenko, N. P.
Chem. Abstr. 1977, 86, 155314.
19
15. Selected data for compound 6: mp 80–82 ꢁC; ½aꢀD ꢁ5.01 (c
1.95 in CHCl3); 1H NMR (200 MHz, CDCl3, TMS):
3
3
d = 0.8 (t, JH,H = 6.8 Hz, 3H; CH3) 1.1–1.5 (m, 6H;
d = 0.85 (t, JH,H = 6.5 Hz, 3H; CH3), 1.10–1.31 (m, 6H;
CH2), 1.86–2.2 (m, 2H; CH2), 2.36 (d, 4JH,H = 2.1 Hz, 1H;
CH), 4.90–5.08 (m, 1H; CH), 7.63–7.90 (m, 4H; CH); 13C
NMR (50 MHz, CDCl3, TMS): d = 13.8, 22.4, 25.7, 30.8,
33.1, 41.2, 71.9, 80.2, 123.2 (2C), 131.5 (2C), 134.0 (2C),
166.6 (2C); GC–MS m/z (%): 226 (13) [M+], 212 (13), 199
(8), 184 (100), 130 (16); FT-IR (diffuse reflectance): 2924,
2118, 1773, 1708, 1387, 1087 cmꢁ1. Elemental Anal. Calcd
(%) for C16H17NO2 (255.3): C, 75.27; H, 6.71; N, 12.53.
Found: C, 74.69; H, 6.55; N, 12.39.
CH2), 1.60–1.81 (m, 1H; CH2), 1.95–2.11 (m, 1H; CH2),
2.82 (dd, 2JH,H = 16.5 Hz, 3JH,H = 5.5 Hz, 1H; CH2), 3.21
(dd, 2JH,H = 16.5 Hz, 3JH,H = 9.3 Hz, 1H; CH2), 4.65 (ddt,
3JH,H = 9.3, 5.5, 4.9 Hz, 1H; CH), 7.76–7.90 (m, 4H; CH),
8.3 (br s, 1H; OH); 13C NMR (50 MHz, CDCl3, TMS):
d = 13.9, 22.3, 25.8, 31.1, 32.2, 36.7, 47.7, 129.2 (2C),
131.6 (2C), 133.9 (2C), 168.3 (2C), 176.3; FT-IR: 3002,
2925, 1773.7, 1712.5, 1376.4 cmꢁ1. Elemental Anal. Calcd
(%) for C16H19NO4 (289.3): C, 62.42; H, 6.62; N, 4.84.
Found: C, 62.28; H, 6.81; N, 4.72.
12. Braga, A. L.; Silveira, C. C.; Reckziegel, A.; Menezes, P.
H. Tetrahedron Lett. 1993, 34, 8041–8042.
16. Formation of 1 by deprotection of 6. Hydrazine hydrate
(0.22 mL, 4.70 mmol) was added to a stirred solution of 6
(0.17 g, 0.58 mmol) in EtOH (10 mL). After stirring for
2 h at 110 ꢁC, the reaction mixture was allowed to slowly
reach room temperature and concentrated. The residue
was treated with 10 mL of 4 N hydrochloric acid and
then the solid was allowed to settle down. Evaporation of
the filtrate gave crude (R)-1 hydrochloride, which was
dissolved in distilled water (5 mL). Hydrogen peroxide
30% w/w (0.5 mL) was then added at rt to decompose the
residual hydrazine. The mixture was then concentrated in
vacuo and the residue dried under reduced pressure to
afford (R)-1 hydrochloride. Selected data for compound
18
13. Selected data for compound 5: oil; ½aꢀD ꢁ90.69 (c 2.48 in
CHCl3); HPLC analysis: Chiralcel OD-H column
(250 · 4 mm, Daicel), eluent: i-PrOH/hexane (2:98) flow
rate: 0.6 mL/min, UV detection at 220 nm; tR 25.8 min:
1
er >99:1; H NMR (200 MHz, CDCl3, TMS): d = 0.7–0.9
(m, 3H; CH3), 1.1–1.4 (m, 6H; CH2), 1.79–1.80 (m, 1H;
2
CH2), 1.95–2.25 (m, 1H; CH2), 3.18 (dd, JH,H = 15.9 Hz,
2
3JH,H = 5.2 Hz, 1H; CH2), 3.6 (dd, JH,H = 15.9 Hz,
3
3JH,H = 9.3 Hz, 1H; CH2), 4.71 (ddt, JH,H = 9.3, 5.2,
4.6 Hz, 1H; CH), 7.25–7.45 (m, 3H; CH), 7.50–7.60 (m,
2H; CH), 7.70–7.80 (m, 2H; CH), 7.80–7.90 (m, 2H; CH);
13C NMR (50 MHz, CDCl3, TMS): d = 13.8, 22.3, 25.8,
31.1, 32.2, 47.8, 49.1, 123.2 (2C), 125.9, 128.9, 129.3 (2C),
131.6 (2C), 133.9 (2C), 135.6 (2C), 168.1 (2C), 197.6; FT-
16
1: mp 110–112 ꢁC (lit,6 mp 103–104 ꢁC); ½aꢀD ꢁ11.16 (c
20
1.35 in H2O). The value reported in the literature6 is ½aꢀD
IR (diffuse reflectance): 2929, 1772, 1711, 1370, 976 cmꢁ1
.
ꢁ16.6 (c 1.10 in H2O). Anal. Calcd for C8H18ClNO2: C,
49.10; H, 9.27; N, 7.16. Found: C, 48.84; H, 9.43; N,
6.84.
Elemental Anal. Calcd (%) for C22H23NO3Se (428.4): C,
61.68; H, 5.41; N, 3.27. Found: C, 61.39; H, 5.77; N, 3.00.