´
Angeles Gama et al. / Tetrahedron: Asymmetry 16 (2005) 1167–1174
1172
À1
1
1
8
034, and 897 cm . H NMR (200 MHz, CDCl ): d
192(92), 133(61), 80(28), and 57(100). HREIMS m/z
calcd for C H NO 339.1825, found 339.1834.
3
.13 (s, 1H), 8.07 (s, 1H), 7.31–7.22 (m, 11H), 6.92 (d,
2
1
25
3
J = 2.0 Hz, 1H), 5.02 (d, J = 7.9 Hz, 1H), 4.49 (d,
J = 7.9 Hz, 1H), 2.11 (br s, 1H), 1.45 (s, 9H), 1.24 (s,
4.12. Data for (S)-(À)-2-tert-butyl-6-[(1-hydroxymethyl-
1
3
1
9
1
1
3
H) ppm; C{ H} NMR (50 MHz, CDCl ): d 167.12,
2,2-dimethyl-propylimino)-methyl]-4-nitro-phenol, 18
3
58.01, 140.30, 140.09, 139.66, 136.63, 128.64, 128.07,
27.94, 127.89, 127.28, 126.31, 117.88, 79.96, 77.0,
4.97, 33.99, 31.78, and 29.36 ppm. Anal. Calcd
25
Yellow solid (0.22 g, 30%); mp 130–133 °C; ½a ¼ À40
D
(c 0.01, CH Cl ); IR (KBr) 3415, 2962, 1632, 1479,
2
1
2
À1
. H NMR (200 MHz, CDCl ): d 8.51 (s,
3
for C H NO : C, 81.08; H, 8.21. Found: C, 81.11;
35
1325 cm
1H), 8.27 (d, J = 2.8 Hz, 1H), 8.15 (d, J = 2.6 Hz, 1H),
.00 (dd, J = 11.4 Hz, J = 2.8 Hz, 1H), 3.66 (t,
2
9
2
H, 8.25.
4
1
2
J = 9.4 Hz, 1H), 3.21 (dd, J = 2.8 Hz, J = 9.4 Hz,
1
1
2
4
5
.9. Data for (1S,2R)-(À)-1-[(3-tert-butyl-2-hydroxy-
1
H) and 1.43 (s, 9H), 1.05 (s, 9H) ppm; C{ H}
3
1
-nitro-benzylidene)-amino]-indan-2-ol, 13
NMR (50 MHz, CDCl ): d 173.97, 168.05, 142.33,
3
25
1
3
38.23, 129.73, 126.01, 117.31, 79.15, 62.23, 36.22,
4.05, 29.53, and 27.32 ppm. Anal. Calcd for
Yellow solid (0.48 g, 40%); mp 72–78 °C; ½a ¼ À29:3
D
(
c 0.50, CH Cl ); IR (KBr): 3419, 3108, 2952, 1638,
2 2
À1
1
600, 1557, 1316, and 748 cm ; H NMR (200 MHz,
C H N O : C, 63.35; H, 8.07. Found: C, 63.41; H,
17 26 2 4
1
8
.10.
CDCl ): d 8.53 (s, 1H), 8.22 (d, 1H, J = 2.80 Hz), 8.16
3
(
d, 1H, J = 3.00 Hz), 7.36–7.20 (m, 4H), 4.95 (d, 1H,
J = 5.2 Hz), 4.76 (q, 1H, J = 5.4 Hz), 3.30 (dd, 1H,
J = 6.0 Hz, J = 16.0 Hz), 3.11 (dd, 1H, J = 5.0 Hz,
J = 16.0 Hz), and 1.42 (s, 9H) ppm; C{ H} NMR
4.13. Data for (S)-(À)-4-bromo-2-tert-butyl-6-
[(1-hydroxymethyl-2,2-dimethyl-propylimino)-methyl]-
phenol 19
1
2
1
3
1
(
50 MHz, CDCl ): d 165.04, 169.10, 140.37, 140.44,
39.24, 138.30, 129.24, 127.48, 127.21, 125.81, 125.54,
3
2
5
1
1
2
2
Yellow solid (0.37 g, 89%); mp 141–143 °C; ½a ¼ À37
D
(c 0.03, CH Cl ); IR (KBr) 3441, 2962, and 1626 cm
H NMR (500 MHz, CDCl ): d 13.95 (s, 1H), 8.22 (s,
À1
25.03, 116.70, 74.92, 73.45, 39.47, 35.21, and
8.89 ppm. EIMS (m/e): 354 [M ] (82), 337(18),
21(43), 207(37), 179(42), 133(100), 105(53), 91(31),
.
2
2
+
1
3
1H), 7.30 (d, J = 2.4 Hz, 1H), 7.22 (d, J = 2.4 Hz, 1H),
3.92 (dd, J = 2.6 Hz, J = 11.10 Hz, 1H), 3.72 (t,
J = 9.7 Hz, 1H), 2.93 (dd, J = 2.8 Hz, J = 9.5 Hz,
and 77(39). HREIMS m/z calcd for C H N O
4
3
2
0
22
2
54.1573, found 354.1579.
1
2
1
3
1
1
H), 1.40 (s, 9H), and 1.00 (s, 9H) ppm; C{ H}
NMR (50 MHz, CDCl ): d 165.60, 159.88, 140.35,
3
4
2
.10. Data for (1R,2S)-(+)-1-[(5-bromo-3-tert-butyl-
-hydoxy-benzylidene)-amino]-indan-2-ol, 14
1
3
32.58, 131.99, 120.01, 110.01, 81.49, 62.62, 35.32,
3.44, 29.40, and 27.27 ppm. Anal. Calcd for
2
5
C H BrNO : C, 57.30; H, 7.30. Found: C, 57.33; H,
1
7
26
2
Yellow liquid (1.13 g, 87%); ½a ¼ þ11:0 (c 0.50,
D
CH Cl ); IR (neat): 3374, 29.51, 1625, 749, and
H NMR (200 MHz, CDCl ): d 8.47 (s,
H), 7.44 (d, J = 2.6 Hz, 1H), 7.32 (d, J = 2.6 Hz, 1H)
.34–7.21 (m, 4H), 4.73 (d, J = 5.2 Hz, 1H), 4.61 (q,
7
.34.
2
2
À1
1
6
1
7
00 cm
;
3
4.14. Data for (S)-(À)-2-tert-butyl-6-[(1-hydroxymethyl-
2,2-dimethyl-propylimino)-methyl]-4-methoxy-phenol, 20
J = 5.2 Hz, 1H), 3.18 (dd, J = 5.6 Hz, J = 15.8 Hz,
1
2
5
H), 3.05 (dd, J = 5.2 Hz, 1H), and 1.36 (s, 9H) ppm;
Yellow solid (0.33 g, 80%); mp 122–125 °C; ½a ¼ À62
D
(c 0.001, CH Cl ); IR (KBr) 3461, 2959, 1631, 1056,
and 783 cm . H NMR (500 MHz, CDCl ): d 8.31 (s,
1H), 6.99 (d, J = 3.2 Hz, 1H), 6.65 (d, J = 3.2 Hz, 1H),
3.94 (dd, J = 3.2 Hz, J = 11.2 Hz, 1H), 3.78 (s, 3H),
1
3
1
C{ H} NMR (50 MHz, CDCl ): d 165.56, 159.57,
3
2
2
À1
1
1
1
3
40.42, 140.05, 139.98, 132.47, 131.69, 128.34, 126.75,
25.18, 124.57, 119.53, 109.54, 74.88, 74.78, 50.28,
9.26, 34.94, 29.22, and 29.00 ppm. EIMS (m/e): 387
3
1
2
+
[
IMS m/z calcd for C H NO Br 387.0834, found
M ] (69), 240(24), 133(100), 103(77), and 77(77). HRE-
3.72 (m, 1H), 2.93 (dd, J = 2.8 Hz, J = 9.2 Hz, 1H),
1 2
1
1.43 (s, 9H), and 0.98 (s, 9H) ppm; C{ H} NMR
3
1
2
0
22
2
3
87.0834.
(50 MHz, CDCl ): d 166.83, 155.32, 151.61, 139.37,
3
1
18.68, 118.06, 112.01, 81.70, 62.76, 56.05, 35.19,
3.42, 29.46, and 27.26 ppm. Anal. Calcd for
3
C H NO : C, 70.34; H, 9.44. Found: C, 70.39; H, 9.45.
4.11. Data for (1R,2S)-(+)-1-[(3-tert-butyl-2-hydroxy-
5-methoxy-benzylidene)-amino]-indan-2-ol, 15
1
8
29
3
2
5
Brown liquid (0.86 g, 82%); ½a ¼ þ27:1 (c 0.50,
4.15. Data for (R)-(+)-2-tert-butyl-6-[(2-hydroxy-1-
phenyl-ethylimino)-methyl]-4-nitro-phenol, 21
D
CH Cl ); IR (neat): 3383, 2953, 1629, 1206, and
; H NMR (200 MHz, CDCl ): d 8.53 (s,
3
H), 7.29–7.17 (m, 4H), 7.01 (d, 1H, J = 5.6 Hz), 4.65
2
2
À1
1
7
52 cm
25
1
Yellow solid (0.13 g, 91%); mp 57–59 °C; ½a ¼ þ19:3
D
(
J = 16.8 Hz, 1H), 3.10 (dd, J = 5.2 Hz, J = 14.0 Hz,
q, J = 5.6 Hz, 1H), 3.77 (s 3H), 3.22 (dd, J = 5.4 Hz,
(c 0.02, CH Cl ); IR (KBr) 3416, 2959, 2871, 1635,
1
2
2
À1
750, and 699 cm . H NMR (200 MHz, CDCl ): d
3
1
2
1
3
2
1
1
H), and 1.38 (s, 9H) ppm; C{ H} NMR (50 MHz,
1
8.50 (s, 1H), 8.20 (d, J = 3.0 Hz, 1H), 8.12 (d,
J = 3.0 Hz, 1H), 7.25–7.41 (m, 5H) 4.58 (t, J = 6.6 Hz,
1H), 3.97 (d, J = 6.6 Hz, 2H), and 1.45 (s, 9H) ppm;
CDCl ): d 167.54, 155.28, 151.59, 141.19, 141.13,
3
1
1
2
39.4, 128.78, 127.27, 125.73, 125.17, 119.19, 118.21,
12.08, 75.74, 75.43, 56.05, 39.79, 35.24, and
9.54 ppm. EIMS (m/e): 339 [M ] (53), 221(32),
1
3
1
C{ H} NMR (50 MHz, CDCl ): d 167.53, 165.76,
3
+
139.89, 138.91, 138.30, 129.28, 128.55, 127.36, 126.75,