I. Kudyba et al. / Tetrahedron: Asymmetry 16 (2005) 2257–2262
2261
4.12. General procedure for the conversion of nitroalkanes
3 into the nitrile oxides 4
Found: C, 74.8; H, 9.0; N, 3.6; IR (film): 2964, 2876,
1729, 1710, 1580, 1496, 1459, 1309, 1293, 1229, 1157,
20
1125, 938, 765, 701, 563; ½a = À82.5( c 0.68, CH2Cl2);
D
To a solution of di-tert-butyl dicarbonate (1.5mmol), 3-
hexene (5mmol), and DMAP (0.15mmol) in acetoni-
trile (5ml), nitroalkane 3 (1 mmol) in acetonitrile
(3 ml) was slowly added at rt. The progress of the reac-
tion was monitored by TLC and, when finished, the
reaction mixture was evaporated and purified on silica
gel (hexane/AcOEt).
1H NMR (500 MHz; CDCl3): d 7.31–7.10 (m, 5H), 5.02–
4.96 (m, 1H), 4.33–4.26 (m, 1H), 2.54–2.47 (m, 1H),
2.16–1.40 (m, 10H), 1.34 (s, 3H), 1.24 (s, 3H), 1.16–
1.05(m, 2H), 0.95(t, J = 7.0, 3H), 0.88 (s, 3H), 0.84
(t, J = 7.5, 3H); 13C NMR (125MHz; CDCl 3): d 159.8,
153.7, 151.1, 128.0, 125.4, 125.2, 89.9, 76.0, 51.4, 50.2,
41.4, 39.8, 34.4, 31.3, 28.0, 27.5, 26.7, 25.9, 24.0, 21.7,
10.6, 9.2.
4.13. 4,5-Diethyl-2-isoxazoline-3-carboxylic acid (20R)-
N-bornane-100,20-sultam imide 5a
4.17. 4,5-Diethyl-2-isoxazoline-3-carboxylic acid
(1R0)-menthyl ester 5e
HRMS-EI: calcd for C18H28O4N2S (M+H)+: 368.1769.
Found: 368.1764; IR (KBr): 2964, 2939, 1670, 1584,
1459, 1344, 1237, 1170, 1138, 1113, 1062, 932, 756, 539,
HRMS-EI: calcd for C24H36O3N (M+Na)+: 332.2202.
Found: 332.2202; IR (KBr): 3408, 2959, 2934, 2873,
1735, 1711, 1581, 1458, 1388, 1372, 1341, 1315, 1229,
1158, 1122, 1096, 955, 936, 914, 823; 1H NMR
(500 MHz; CDCl3): 4.91–4.85(m, 1H), 4.43–4.39 (m,
1H), 3.12–3.08 (m, 1H), 2.08–2.02 (m, 1H), 1.98–1.85
(m, 1H), 1.81–1.48 (m, 8H), 1.17–1.04 (m, 2H), 0.97 (t,
J = 7.5, 3H), 0.93–0.86 (m, 10H), 0.79–0.77 (m, 3H);
13C NMR (125MHz; CDCl 3): d 160.5, 153.8, 89.7,
76.0, 52.2, 46.7, 40.6, 34.1, 31.4, 28.0, 26.3, 24.0, 23.5,
23.2, 20.7, 16.3, 10.6, 9.1.
1
494; H NMR (500 MHz; CDCl3): d 4.39–4.35(m, 1H),
4.23–4.20 (m, 0.58H), 4.14–4.11 (m, 0.42H), 3.49–3.43
(m, 2H), 3.31–3.27 (m, 0.58H), 3.09–3.06 (m, 0.42H),
2.12–1.84 (m, 5H), 1.76–1.35 (m, 6H), 1.23 (s, 3H), 0.99
(s, 3H), 0.98–0.90 (m, 6H); 13C NMR (125MHz;
CDCl3): d 161.2, 155.7, 89.5, 65.8, 53.1, 52.8, 48.9, 47.9,
4.4, 39.5, 33.3, 28.0, 26.3, 24.0, 21.5, 19.9, 11.2, 9.3.
4.14. 4,5-Diethyl-2-isoxazoline-3-carboxylic acid (20R)-
N-70,70-dimethylnorbornane-(10S,20R)-oxazolidinone
imide 5b
4.18. X-ray data
HRMS-EI: calcd for C18H28O4N2S (M+Na)+: 357.1797.
Found: 357.1790; IR (KBr): 3431, 2966, 2939, 2879,
1791, 1696, 1555, 1458, 1367, 1322, 1303, 1292, 1252,
1229, 1174, 1074, 1051, 1007, 916, 883, 808, 780, 762;
1H NMR (500 MHz; CDCl3): d 4.39–4.35(m, 1H),
3.27–3.23 (m, 1H), 2.83–2.73 (m, 1H), 2.36–2.26 (m,
1H), 2.12–2.02 (m, 1H), 1.92–1.58 (m, 6H), 1.40–1.25
(m, 3H), 1.22 (s, 1.7H), 1.20 (s, 1.3H), 1.07 (s, 3H),
1.02–0.95(m, 6H); 13C NMR (125MHz; CDCl 3): d
162.7, 155.1, 154.1, 89.2, 85.5, 72.6, 54.8, 53.7, 48.2,
42.5, 34.6, 27.8, 25.8, 24.5, 21.5, 19.1, 11.3, 9.1.
X-ray single-crystal diffraction experiments were carried
out on a Kuma KM4CCD j-axis diffractometer using
˚
Mo Ka radiation (0.7107 A). The program used to solve
and refine was SHELX-97.
C12H20N2O5S1 2a, M = 304.36, orthorhombic, a =
8.0503(13), b = 11.5239(16), c = 15.2014(18), a = 90,
b = 90, c = 90ꢂ, space group P212121, Z = 1, Dcalcd
=
0.358 Mg/m3, l(Mo Ka) = 0.063 mmÀ1, 7260 reflections
measured, 3340 [Rint = 0.0966] unique reflections, which
were used in all calculations. Data/restraints/parameters
3340/0/193. The final R1 = 0.0612 (all data), 0À.034(11).
˚
4.15. 4,5-Diethyl-2-isoxazoline-3-carboxylic acid N,N-
dicyclohexyl-100-sulfamoyl-(2R0)-O-isobornane ester 5c
Residual electron density 0. 556 and À0.949 e A
.
C12H16N2O4 2b, M = 252.27, orthorhombic, a =
6.9310(4), b = 8.8942(5), c = 20.0216(11), a = 90, b = 90,
c = 90ꢂ, space group P212121, Z = 4, Dcalcd = 1.358 Mg/
m3, l(Mo Ka) = 0.103 mmÀ1, 17511 reflections mea-
sured, 1925[ Rint = 0.0329] unique reflections, which
were used in all calculations. Data/restraints/parameters
HRMS-EI: calcd for C30H50O5N2SNa (M+Na)+:
573.3338. Found: 573.3334; IR (KBr): 3418, 2933,
2854, 1718, 1455, 1394, 1323, 1227, 1165, 1142, 1106,
1
1048, 981, 941, 853, 823, 773, 642, 576, 524; H NMR
(500 MHz; CDCl3): d 5.12–5.05 (m, 1H), 4.39–4.31 (m,
1H), 3.43 (d, J = 13.0 Hz, 0.45H), 3.41 (d, J = 13.0 Hz,
0.55H), 3.30–3.17 (m, 2H), 3.17–3.10 (m, 0.45H), 3.10–
3.07 (m, 0.55H), 2.63 (d, J = 13.0 Hz, 0.55H), 2.61 (d,
J = 13.0 Hz, 0.45H), 2.08–1.48 (m, 15H), 1.44–1.05 (m,
7H), 1.04 (s, 3H), 0.99–0.91 (m, 5H), 0.88 (s, 3H); 13C
NMR (125MHz; CDCl 3): d 159.9, 153.9, 89.6, 79.7,
57.3, 53.4, 52.6, 49.6, 49.1, 44.5, 39.5, 32.4, 30.2, 28.2,
26.3, 26.1, 25.2, 24.2, 20.4, 20.0, 10.7, 9.1.
1925/0/228. The final R1 = 0.0276 (all data),À30.1(9).
˚
Residual electron density 0.212 and À0.240 e A
.
C24H40N2O5S1 2c, M = 468.64, monoclinic, a = 11.216(2),
b = 9.2187(18), c = 12.435(3), a = 90, b = 96.81(3), c =
90ꢂ, space group P21, Z = 2, Dcalcd = 1.219 Mg/m3,
l(Mo Ka) = 0.162 mmÀ1. The final R1 = 0.0510 (all
data), À0.0À13(15). Residual electron density 0.133 and
˚
À0.128 e A
.
4.16. 4,5-Diethyl-2-isoxazoline-3-carboxylic acid (10R)-
80-phenylmenthyl ester 5d
C12H21NO3 2e, M = 286.35, monoclinic, a = 7.2380(14),
b = 11.293(2), c = 8.7830(18), a = 90, b = 107.23(3),
c = 90ꢂ, space group P21, Z = 2, Dcalcd = 1.101 Mg/m3,
l(Mo Ka) = 0.078 mmÀ1. The final R1 = 0.0390 (all
HRMS-EI: calcd for C24H36O3N (M+H)+: 386.2695.
Found: 386.2687. Anal. Calcd C, 74.8; H, 9.1; N, 3.6.