Y. Liu et al. / Tetrahedron 58.2002) 3159±3170
3167
compound was prepared from the corresponding N-oxide
re¯uxing in toluene for 24 h in the presence of ZnCl2 and
isolated as a white solid, 30% yield: mp 167±1698C;
as a white solid ;51% yield) along with 10b ;white solid,
20
30%): For 11a: mp 118±1208C; [a]D 1135.0 ;c 0.15,
1
CHCl3); H NMR ;CDCl3, 300 Hz) d 1.80±1.89 ;m, 2H),
20
1
[a]D 177.0 ;c 0.22, CHCl3); H NMR ;CDCl3, 300 Hz)
d 0.92 ;d, J6.6 Hz, 3H), 0.96 ;d, J6.3 Hz, 3H), 1.41±
1.63 ;m, 3H), 1.75±1.92 ;m, 2H), 2.15 ;dd, J3.0, 13.8 Hz,
1H), 2.66±2.78 ;m, 1H), 2.86±3.00 ;m, 1H), 3.49 ;dd,
J4.5, 9.6 Hz, 1H), 3.76 ;d, J12.9 Hz, 1H), 3.96 ;d,
J15.3 Hz, 1H), 3.90±3.99 ;m, 1H), 4.25 ;s, 1H), 4.52±
4.59 ;m, 1H), 7.03 ;t, J7.5 Hz, 1H), 7.25±7.45 ;m, 7H),
8.51 ;d, J8.1 Hz, 1H); 13CH NMR ;CDCl3, 100 Hz) d
18.6, 21.5, 26.1, 30.0, 31.7, 40.1, 60.4, 62.4, 64.4, 71.4,
120.3, 125.8, 126.8, 127.8, 128.8, 131.3, 132.0, 132.5,
136.1, 147.0; HRMS calcd for C23H29N3O5S ;MH1)
460.1908, found 460.1898.
2.36 ;s, 3H), 2.49 ;d, J4.5 Hz, 1H), 2.74±2.80 ;m, 1H),
2.93 ;dd, J10.5, 13.5 Hz, 1H), 3.22 ;dd, J4.5, 13.5 Hz,
1H), 3.39 ;ddd, J3.9, 9.9, 13.5 Hz, 1H), 3.53 ;dd, J2.4,
7.8 Hz, 1H), 3.80 ;dt, J13.5, 4.5 Hz, 1H), 4.04 ;dd, J6.3,
7.8 Hz, 1H), 4.21 ;dd, J4.8, 10.5 Hz, 1H) 7.21±7.34 ;m,
5H), 7.57±7.67 ;m, 3H), 8.08±8.11 ;m, 1H); 13CH NMR
;CDCl3, 75 Hz) d 25.6, 37.6, 39.7, 40.2, 43.4, 54.4, 66.7,
70.9, 123.7, 127.0, 128.8, 129.0, 130.5, 131.6, 133.1, 133.7,
137.5, 148.3; HRMS calcd for C20H23N3O5S ;MH1)
418.1438, found 418.1432.
4.5.12. 7-Isopropyl-1,3,3-trimethyl-6-.2-nitro-benzene-
sulfonyl)-octahydro-isoxazolo[3,4-c]pyridine .11b). The
title compound was prepared from the corresponding
N-oxide re¯uxing in toluene for 24 h in the presence of
ZnCl2 and isolated as a white solid, 52% yield: mp 123±
4.5.8. 2-tert-Butoxymethyl-8-methyl-3-.2-nitro-benzene-
sulfonyl)-7-oxa-3,8-diaza-bicyclo[4.2.1]nonane
.10h).
20
Light yellow syrup, 17% yield: [a]D 112.4 ;c 0.80,
CHCl3); 1H NMR ;CDCl3, 300 Hz) d 0.95 9 ;s, 9H),
1.60±1.74 ;m, 2H), 2.39 ;d, J12.6 Hz, 1H), 2.49±2.58
;m, 1H), 2.97 ;s, 1H), 3.14 ;dd, J6.9, 8.4 Hz, 1H), 3.39±
3.59 ;m, 3H), 3.80 ;d, J15.3 Hz, 1H), 3.99 ;dd, J6.9,
13.2 Hz, 1H), 4.59 ;bt, J5.7 Hz, 1H), 7.60±7.70 ;m,
3H), 8.09±8.11 ;m, 1H); 13CH NMR ;CDCl3, 100 Hz) d
27.9, 34.7, 36.4, 41.1, 49.5, 59.4, 60.0, 66.9, 73.6, 77.1,
124.7, 132.0, 132.2, 133.6, 135.5, 148.6; HRMS calcd for
C18H27N3O6S ;MH1) 414.1700, found 414.1691.
20
1
1258C; [a]D 1116 ;c 0.33, CHCl3); H NMR ;CDCl3,
300 Hz) d 0.98 ;d, J6.9 Hz, 3H), 1.09 ;s, 3H), 1.11 ;d,
J5.1 Hz, 3H), 1.29 ;s, 3H), 1.42±1.49 ;m, 1H), 1.65 ;ddd,
J4.5, 13.2, 17.4 Hz, 1H), 1.88±2.00 ;m, 1H), 2.14±2.22
;m, 1H), 2.96 ;dd, J2.4, 15.0 Hz, 1H), 3.62 ;d, J10.2 Hz,
1H), 3.90 ;bd, J14.4 Hz, 1H), 7.47±7.53 ;m, 1H), 7.61±
7.66 ;m, 1H), 8.29±8.34 ;m, 1H); 13CH NMR ;CDCl3,
75 Hz) d 20.1, 21.5, 22.6, 23.2, 29.9, 31.0, 40.5, 45.5,
46.5, 59.8, 66.7, 81.3, 123.7, 131.5, 131.6, 133.6, 134.7,
149.1; HRMS calcd for C18H27N3O5S ;MH1) 398.1751,
found 398.1753.
4.5.9. [8-Methyl-3-.2-nitro-benzenesulfonyl)-7-oxa-3,8-
diaza-bicyclo[4.2.1]non-2-yl]-acetic acid tert-butyl ester
20
.10i). White solid, 46% yield: mp 153±1558C; [a]D
4.5.13. 1,7-Dimethyl-6-.2-nitro-benzenesulfonyl)-octa-
hydro-isoxazolo[3,4-c]pyridine .11c). The title compound
was prepared from the corresponding N-oxide re¯uxing in
toluene for 24 h in the presence of ZnCl2 and isolated as a
1
148.0 ;c 0.15, CHCl3); H NMR ;CDCl3, 300 Hz) ; 1.38
;s, 9H), 1.59±1.69 ;m, 2H), 1.94 ;dd, J3.3, 16.2 Hz, 1H),
2.36 ;d, J12.6 Hz, 1H), 2.50±2.57 ;m, 1H), 2.60 ;s, 3H),
3.14 ;dd, J11.1, 15.9 Hz, 1H), 3.29 ;ddd, J3.9, 11.4,
15.3 Hz, 1H), 3.62 ;dd, J6.0, 8.1 Hz, 1H), 3.76 ;d, J
15.0 Hz, 1H), 4.27±4.34 ;m, 1H), 4.59±4.63 ;m, 1H),
7.60±7.73 ;m, 3H), 8.03±8.06 ;m 1H); 13CH NMR
;CDCl3, 75 Hz) d 28.0, 34.1, 34.8, 35.8, 40.1, 48.5, 55.6,
66.5, 76.2, 80.9, 124.2, 130.9, 131.7, 133.6, 133.9, 147.7,
170.2; MS calcd for C19H27N3O7S1Na 464, found 464.
Anal. calcd for: C19H27N3O7S: C, 51.69; H, 6.16; N, 9.52.
Found C, 52.04; H, 6.55; N, 9.90.
20
white solid ;52% yield: mp 115±1178C; [a]D 124.0 ;c
1
0.23, CHCl3); H NMR ;CDCl3, 300 Hz) d 1.38 ;d, J
6.9 Hz, 3H), 1.73±1.92 ;m, 2H), 2.47 ;dd, J1.8, 5.7 Hz,
1H), 2.59 ;s, 3H), 2.66±2.74 ;m, 1H), 3.29 ;ddd, J3.3,
11.1, 13.8 Hz, 1H), 3.54 ;dd, J2.1, 7.5 Hz, 1H), 3.70 ;dt,
J13.5, 4.5 Hz, 1H), 4.04±4.14 ;m, 2H), 7.59±7.69 ;m,
3H), 8.16±8.21 ;m, 1H); 13CH NMR ;CDCl3, 75 Hz) d
19.7, 26.2, 38.4, 39.1, 44.7, 48.9, 71.2, 71.4, 124.6, 131.2,
132.2, 133.8, 134.6, 148.8; HRMS calcd for C14H19N3O5S
;MH1) 342.1125 found 342.1132.
4.5.10. [8-Benzyl-3-.2-nitro-benzenesulfonyl)-7-oxa-3,8-
diaza-bicyclo[4.2.1]non-2-yl]-acetic acid tert-butyl ester
4.5.14. 1-Benzyl-7-methyl-6-.2-nitro-benzenesulfonyl)-
octahydro-isoxazolo[3,4-c]pyridine .11d). The title com-
pound was prepared from the corresponding N-oxide
re¯uxing in toluene for 24 h in the presence of ZnCl2 and
isolated as a white solid ;32% yield): mp 162±1648C;
[a]D 111 ;c 0.17, CHCl3); H NMR ;CDCl3, 300 Hz) d
1.38 ;d, J6.9 Hz, 3H), 1.71±1.79 ;m, 1H), 1.83±1.97 ;m,
1H), 2.68±2.75 ;m, 1H), 2.81 ;dd, J1.5, 5.4 Hz, 1H), 3.29
;ddd, J3.0, 11.1, 13.8 Hz, 1H), 3.58 ;d, J7.8 Hz, 1H),
3.71 ;dt, J18.3, 4.8 Hz, 1H), 3.79 ;d, J14.1 Hz, 1H), 4.03
;dd, J5.1, 7.8 Hz, 1H), 4.08 ;d, J14.1 Hz, 1H), 4.18 ;dd,
J7.2, 14.1 Hz, 1H), 7.18±7.29 ;m, 5H), 7.39±7.54 ;m,
3H), 8.23 ;d, J8.1 Hz, 1H); 13CH NMR ;CDCl3, 75 Hz)
d 18.9, 25.0, 37.4, 38.8, 48.7, 61.1, 67.9, 70.6, 123.8, 127.0,
128.1, 128.7, 130.4, 131.5, 132.8, 134.0, 137.2, 148.1;
HRMS calcd for C20H23N3O5S ;MH1) 417.1367. Found
417.1380.
20
.10j). White solid, 38% yield: mp 142±1438C; [a]D
1
19.00 ;c 0.24, CHCl3); H NMR ;CDCl3, 300 Hz) d 1.35
;s, 9H), 1.57±1.75 ;m, 2H), 2.00 ;dd, J3.6, 16.5 Hz, 1H),
2.34±2.38 ;m, 1H), 3.20±3.39 ;m, 2H), 3.75±3.90 ;m, 4H),
4.33±4.39 ;m, 1H), 4.60 ;s, 1H), 7.23±7.38 ;m, 5H), 7.61±
7.71 ;m, 3H), 8.04±8.07 ;m 1H); 13CH NMR ;CDCl3,
75 Hz) d 28.2, 35.0, 35.4, 35.5, 40.4, 56.0, 64.7, 64.8,
76.4, 81.2, 124.4, 127.6, 128.5, 129.3, 131.8, 131.9, 133.8,
134.2, 137.7, 148.0, 170.5; MS calcd for C25H31N3O7S1Na
540, found 540. Anal. calcd for C25H31N3O7S: C, 58.01; H,
6.04; N, 8.12. Found C, 57.92; H, 5.99; N, 8.22.
20
1
4.5.11. 7-Benzyl-1-methyl-6-.2-nitro-benzenesulfonyl)-
octahydro-isoxazolo[3,4-c]pyridine .11a). The title com-
pound was prepared from the corresponding N-oxide re¯ux-
ing in toluene for 24 h in the absence of ZnCl2 and isolated