S. Krompiec et al. / Tetrahedron 68 (2012) 6018e6031
6029
(400 MHz, CDCl3)
d
¼1.09 ppm (d, J¼7.6 Hz, 3H, CH3CH), 2.61 (dd,
Compound trans-2-4k 1H NMR (400 MHz, CDCl3)
d
¼1.22 ppm (d,
J¼5.1 Hz, J¼2.6 Hz, 1H, OCH2CHCH2), 2.79 (dd, J¼5.1 Hz, J¼4.4 Hz,
1H, OCH2CHCH2), 3.19e3.25 (m, 1H, OCH2CHCH2), 3.47 (dd,
J¼11.5 Hz, J¼7.0 Hz, 1H, OCH2CHCH2), 3.85 (dq, J¼6.6 Hz, J¼7.6 Hz,
1H, CH3CH), 4.14 (dd, J¼11.5 Hz, J¼2.8 Hz, 1H, OCH2CHCH2), 5.60 (d,
J¼6.6 Hz, 1H, OCHO), 7.29e7.39 (m, 3H, CAreH). 13C NMR (100 MHz,
J¼7.7 Hz, 3H, CH3CH), 1.55e1.92 (m, 6H, CH2CH2CH2), 3.61 (qd,
J¼7.7 Hz, J¼1.5 Hz, 1H, CH3CH), 3.81e3.93 (m, 2H, OCH2), 5.10e5.12
(m, 1H, OCHOCHOCH2), 5.72 (d, J¼1.5 Hz, 1H, OCHOCHOCH2),
7.28e7.68 (m, 3H, CAreH). 13C NMR (100 MHz, CDCl3)
d
¼11.6 ppm
(CH3CH), 22.9 (CH2CH2CH2), 25.6 (CH2CH2CH2), 29.8 (CH2CH2CH2),
48.8 (CH3CH), 52.1 (OCH2), 95.8 (OCHOCHOCH2), 104.9 (OCHO-
CHOCH2), 128.3, 128.4, 131.2, 135.8 (CAr), 159.3 (C]N). IR (film):
3078, 2943, 2871, 2746, 2234, 2056, 1728, 1560, 1352, 1201, 1122,
1036, 967, 905, 856, 788, 723, 697 cmꢀ1. MS (ESIþ) m/z 352.0
[MþNa]þ, HRMS (ESIþ): calcd for C15H1735Cl2NO3Na [MþNa]þ
352.0478 found 352.0479.
CDCl3)
d
¼7.4 ppm (CH3CH), 44.4 (OCH2CHCH2), 48.2 (OCH2CHCH2),
50.5 (CH3CH), 69.7 (OCH2CHCH2), 103.9 (OCHO), 128.2, 131.2, 132.1,
135.5 (CAr), 159.3 (C]N). Compound cis-2-4j 1H NMR (400 MHz,
CDCl3)
d
¼1.13 ppm (d, J¼7.6 Hz, 3H, CH3CH), 2.61 (dd, J¼5.1 Hz,
J¼2.6 Hz, 1H, OCH2CHCH2), 2.79 (dd, J¼5.1 Hz, J¼4.4 Hz, 1H,
OCH2CHCH2), 3.19e3.25 (m, 1H, OCH2CHCH2), 3.50 (dd, J¼11.5 Hz,
J¼6.8 Hz,1H, OCH2CHCH2), 3.86 (dq, J¼6.6 Hz, J¼7.6 Hz,1H, CH3CH),
4.14 (dd, J¼11.5 Hz, J¼2.8 Hz,1H, OCH2CHCH2), 5.65 (d, J¼6.6 Hz,1H,
OCHO), 7.29e7.39 (m, 3H, CAreH). 13C NMR (100 MHz, CDCl3)
4.4.16. 3-(2,6-Dichlorophenyl)-5-(O-a-D-galactopyranosyl)-4-
methyl-4,5-dihydroisoxazole (4l). Obtained as light yellow oil
d
¼7.4 ppm (CH3CH), 44.2 (OCH2CHCH2), 48.2 (OCH2CHCH2), 50.9
(320 mg, 58%); trans/cis¼0.21. Compound cis-1-4l 1H NMR (400 MHz,
(CH3CH), 69.7 (OCH2CHCH2),103.8 (OCHO),128.3,131.2,132.0,135.6
D2O)
d
¼1.09 ppm (d, J¼7.1 Hz, 3H, CH3CH), 3.46e3.96 (m, 6H, CH(OH)
(CAr), 159.4 (C]N). Compound trans-1-4j 1H NMR (400 MHz, CDCl3)
CH(OH)CH(OH)CHCH2(OH)), 3.92 (dq, J¼6.6 Hz, J¼7.1 Hz,1H, CH3CH),
d
¼1.21 ppm (d, J¼7.7 Hz, 3H, CH3CH), 2.75 (dd, J¼5.2 Hz, J¼4.2 Hz,
5.32 (d, J¼3.7 Hz, 1H, CH(OH)CHOCH), 5.96 (d, J¼6.6 Hz, 1H, OCHO),
1H, OCH2CHCH2), 2.84 (dd, J¼5.2 Hz, J¼2.5 Hz, 1H, OCH2CHCH2);
3.19e3.25 (m, 1H, OCH2CHCH2), 3.64 (qd, J¼7.7 Hz, J¼1.4 Hz, 1H,
CH3CH), 3.89 (dd, J¼12.0 Hz, J¼3.0 Hz, 1H, OCH2CHCH2), 3.99 (dd,
J¼12.0 Hz, J¼3.5 Hz, 1H, OCH2CHCH2), 5.43 (d, J¼1.4 Hz, 1H, OCHO),
7.31e7.47 (m, 3H, CAreH). 13C NMR (100 MHz, DMSO-d6)
d¼7.0 ppm
(CH3CH), 42.1 (CH3CH), 59.6 (CH2OHegalactopyranose), 67.6
(CHOHegalactopyranose), 68.3 (CHOHegalactopyranose), 69.4
(CHOHegalactopyranose), 71.5 (CHCH2OHegalactopyranose), 79.2
(OCHOegalactopyranose), 99.1 (OCHO), 128.4, 129.4, 131.3, 134.4
(CAr), 158.5 (C]N). Compound cis-2-4l 1H NMR (400 MHz, D2O)
7.29e7.39 (m, 3H, CAreH). 13C NMR (100 MHz, CDCl3)
d¼13.7 ppm
(CH3CH), 44.4 (OCH2CHCH2), 50.8 (CH3CH), 52.1 (OCH2CHCH2), 67.0
(OCH2CHCH2), 109.4 (OCHO), 128.3, 131.1, 132.0, 135.5 (CAr), 159.2
(C]N). Compound trans-2-4j 1H NMR (400 MHz, CDCl3)
d
¼1.06 ppm (d, J¼7.2 Hz, 3H, CH3CH), 3.46e3.96 (m, 6H, CH(OH)
CH(OH)CH(OH)CHCH2(OH)), 3.96 (dq, J¼6.4 Hz, J¼7.2 Hz,1H, CH3CH),
5.26 (d, J¼3.7 Hz, 1H, CH(OH)CHOCH), 5.88 (d, J¼6.4 Hz, 1H, OCHO),
d
¼1.20 ppm (d, J¼7.6 Hz, 3H, CH3CH), 2.75 (dd, J¼5.2 Hz, J¼4.2 Hz,
1H, OCH2CHCH2), 2.84 (dd, J¼5.2 Hz, J¼2.5 Hz, 1H, OCH2CHCH2),
3.19e3.25 (m, 1H, OCH2CHCH2), 3.59 (qd, J¼7.6 Hz, J¼1.4 Hz, 1H,
CH3CH), 3.90 (dd, J¼12.0 Hz, J¼3.0 Hz, 1H, OCH2CHCH2), 4.00 (dd,
J¼12.0 Hz, J¼3.6 Hz, 1H, OCH2CHCH2), 5.39 (d, J¼1.4 Hz, 1H, OCHO),
7.31e7.47 (m, 3H, CAreH). 13C NMR (100 MHz, DMSO-d6)
d¼8.4 ppm
(CH3CH), 45.6 (CH3CH), 60.6 (CH2OHegalactopyranose), 67.7
(CHOHegalactopyranose), 68.3 (CHOHegalactopyranose), 69.4
(CHOHegalactopyranose), 72.3 (CHCH2OHegalactopyranose), 79.6
(OCHOegalactopyranose), 99.7 (OCHO), 128.6, 129.1, 131.4, 134.1
(CAr), 158.7 (C]N). Compound trans-1-4l 1H NMR (400 MHz, D2O)
7.29e7.39 (m, 3H, CAreH). 13C NMR (100 MHz, CDCl3)
d¼13.6 ppm
(CH3CH), 44.5 (OCH2CHCH2), 50.4 (CH3CH), 52.0 (OCH2CHCH2), 66.9
(OCH2CHCH2), 109.5 (OCHO), 128.4, 131.3, 131.9, 135.5 (CAr), 159.2
(C]N). IR (film): 3419, 3080, 2976, 2936, 2879, 2237, 1738, 1678,
1581, 1560, 1432, 1278, 1195, 1083, 852, 788, 729, 698 cmꢀ1. MS
(ESIþ) m/z 324.0 [MþNa]þ, HRMS (ESIþ): calcd for
C13H1335Cl2NO3Na [MþNa]þ 324.0165 found 324.0152.
d
¼1.04 ppm (d, J¼6.8 Hz, 3H, CH3CH), 3.46e3.96 (m, 6H, CH(OH)
CH(OH)CH(OH)CHCH2(OH)), 4.10 (qd, J¼6.8 Hz, J¼1.5 Hz,1H, CH3CH),
5.24 (d, J¼3.70 Hz, 1H, CH(OH)CHOCH), 5.75 (d, J¼1.5 Hz, 1H, OCHO),
7.31e7.47 (m, 3H, CAreH). 13C NMR (100 MHz, DMSO-d6)
d¼12.1 ppm
(CH3CH), 47.4 (CH3CH), 60.6 (CH2OHegalactopyranose), 66.2
(CHOHegalactopyranose), 68.1 (CHOHegalactopyranose), 68.7
(CHOHegalactopyranose), 71.3 (CHCH2OHegalactopyranose), 95.1
(OCHOegalactopyranose), 103.8 (OCHO), 128.0, 129.2, 131.9, 134.5
(CAr), 165.0 (C]N). Compound trans-2-4l 1H NMR (400 MHz, D2O)
4.4.15. 3-(2,6-Dichlorophenyl)-4-methyl-5-(tetrahydro-2H-pyran-2-
yloxy)-4,5-dihydroisoxazole (4k). Obtained as light yellow oil
(252 mg, 62%); trans/cis¼0.67; Rf (CH2Cl2)¼0.65. Compound cis-1-
4k 1H NMR (400 MHz, CDCl3)
d
¼1.08 ppm (d, J¼7.6 Hz, 3H, CH3CH),
d
¼1.02 ppm (d, J¼7.0 Hz, 3H, CH3CH), 3.46e3.96 (m, 6H, CH(OH)
1.55e1.92 (m, 6H, CH2CH2CH2), 3.58 (dq, J¼6.9 Hz, J¼7.6 Hz, 1H,
CH3CH), 3.81e3.93 (m, 2H, OCH2), 4.98e4.99 (m, 1H, OCHO-
CHOCH2), 5.81 (d, J¼6.9 Hz, 1H, OCHOCHOCH2), 7.28e7.68 (m, 3H,
CH(OH)CH(OH)CHCH2(OH)), 4.05 (qd, J¼7.0 Hz, J¼0.9 Hz,1H, CH3CH),
5.31 (d, J¼3.7 Hz, 1H, CH(OH)CHOCH), 5.69 (d, J¼0.9 Hz, 1H, OCHO),
7.31e7.47 (m, 3H, CAreH). 13C NMR (100 MHz, DMSO-d6)
d¼13.4 ppm
CAreH). 13C NMR (100 MHz, CDCl3)
d
¼8.5 ppm (CH3CH), 22.8
(CH3CH) 47.6 (CH3CH), 60.6 (CH2OHegalactopyranose), 67.5
(CHOHegalactopyranose), 68.2 (CHOHegalactopyranose), 68.8
(CHOHegalactopyranose), 71.4 (CHCH2OHegalactopyranose), 97.9
(OCHOegalactopyranose), 105.9 (OCHO), 128.3, 129.1, 131.9, 134.5
(CAr),165.3 (C]N). IR (film): 3399, 3074, 2922,1605,1581,1560,1431,
1384, 1328, 1243, 1149, 1074, 1037, 911, 870, 786, 723, 693 cmꢀ1. MS
(CH2CH2CH2), 25.5 (CH2CH2CH2), 32.1 (CH2CH2CH2), 46.9 (CH3CH),
63.4 (OCH2), 94.9 (OCHOCHOCH2), 98.8 (OCHOCHOCH2), 128.2,
128.5, 131.2, 135.9 (CAr), 159.4 (C]N). Compound cis-2-4k 1H NMR
(400 MHz, CDCl3)
d¼1.16 ppm (d, J¼7.5 Hz, 3H, CH3CH), 1.55e1.92
(m, 6H, CH2CH2CH2), 3.53e3.64 (m, 2H, OCH2), 3.89 (dq, J¼6.6 Hz,
J¼7.5 Hz, 1H, CH3CH), 5.18e5.20 (m, 1H, OCHOCHOCH2), 5.93 (d,
J¼6.6 Hz, 1H, OCHOCHOCH2), 7.28e7.68 (m, 3H, CAreH). 13C NMR
(ESIþ)
m/z¼430.0
[MþNa]þ,
HRMS
(ESIþ):
calcd
for
C16H1935Cl2NO7Na [MþNa]þ 430.0431 found 430.0421.
(100 MHz, CDCl3)
d
¼7.6 ppm (CH3CH), 22.8 (CH2CH2CH2), 25.4
(CH2CH2CH2), 31.7 (CH2CH2CH2), 48.0 (CH3CH), 62.6 (OCH2), 94.8
(OCHOCHOCH2), 99.0 (OCHOCHOCH2), 128.3, 128.4, 131.2, 135.8
(CAr), 159.5 (C]N). Compound trans-1-4k 1H NMR (400 MHz,
4.4.17. 4-Methyl-5-phenoxy-3-phenyl-4,5-dihydroisoxazol
(9f). Obtained as white solid (110 mg, 34%); mp¼68 ꢁC; trans/
cis¼1.00; Rf (toluene)¼0.58. Compound cis-9f 1H NMR (400 MHz,
CDCl3)
d
¼1.27 ppm (d, J¼7.3 Hz, 3H, CH3CH), 1.55e1.92 (m, 6H,
CDCl3)
d
¼1.44 ppm (d, J¼7.5 Hz, 3H, CH3CH), 3.94 (dq, J¼7.1 Hz,
CH2CH2CH2), 3.53e3.64 (m, 2H, OCH2), 3.84 (qd, J¼7.3 Hz, J¼2.0 Hz,
1H, CH3CH), 5.02e5.04 (m, 1H, OCHOCHOCH2), 5.58 (d, J¼2.0 Hz,
1H, OCHOCHOCH2), 7.28e7.68 (m, 3H, CAreH). 13C NMR (100 MHz,
J¼7.5 Hz, 1H, CH3CH), 6.18 (d, J¼7.1 Hz, 1H, OCHO), 7.04e7.64 (m,
5Hþ5H, CAreH). 13C NMR (100 MHz, CDCl3)
¼9.8 ppm (CH3CH),
d
46.2 (CH3CH), 102.7 (OCHO), 117.0, 122.7, 127.5, 128.6, 128.7, 129.5,
CDCl3)
d
¼12.1 ppm (CH3CH), 23.1 (CH2CH2CH2), 25.6 (CH2CH2CH2);
130.1, 156.7 (CAr), 161.5 (C]N). Compound trans-9f 1H NMR
30.4 (CH2CH2CH2), 48.1 (CH3CH), 53.3 (OCH2), 95.7 (OCHOCHOCH2),
104.6 (OCHOCHOCH2), 128.0, 128.5, 131.2, 135.9 (CAr), 159.1 (C]N).
(400 MHz, CDCl3)
J¼7.6 Hz, J¼0.9 Hz, 1H, CH3CH), 5.88 (d, J¼0.9 Hz, 1H, OCHO),
d
¼1.38 ppm (d, J¼7.6 Hz, 3H, CH3CH), 3.81 (qd,