M.-Y. Chang et al. / Tetrahedron 58 -2002) 5075±5080
5079
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4.4.4. Methyl 5-benzylcarbamoyl-2-hydroxy-5-.4-phenyl-
sulfonyl)-1-cyclohexene-1-carboxylate. Mp146±1478C;
IR 8CHCl3) 3426, 3029, 1733, 1677 cm21; ESI-MS:
C22H24NO6S m/z 8%)91 8100), 430 8M111, 18); HRMS
8ESI, M111) calcd for C22H24NO6S 430.1325, found
found 496.1678; H NMR 8300 MHz, CDCl3): d 12.08 8s,
1H), 8.25 8br s, 1H), 7.61 8d, J7.5 Hz, 1H), 7.44 8d, J
8.4 Hz, 2H), 7.34 8d, J8.1 Hz, 1H), 7.25±7.11 8m, 4H),
7.04 8d, J6.6 Hz, 1H), 6.78 8t, J8.1 Hz, 1H), 3.66 8s, 3H),
3.63±3.55 8m, 2H), 3.02 8t, J6.6 Hz, 2H), 2.90 8d, J
15.9 Hz, 1H), 2.78 8d, J15.9 Hz, 1H), 2.37 8s, 3H),
2.36±2.28 8m, 3H), 2.15±2.09 8m, 1H); 13C NMR
875 MHz, CDCl3): d 171.63, 170.05, 164.98, 145.59,
136.42, 131.48, 129.69 82£), 129.66 82£), 126.92, 122.45,
122.09, 119.37, 118.50, 112.05, 111.34, 94.20, 70.12, 51.65,
40.48, 26.13, 25.23, 24.69, 24.53, 21.64.
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430.1323; H NMR 8400 MHz, CDCl3): d 12.08 8s, 1H),
7.62±7.24 8m, 10H), 7.08 8br s, 1H), 4.47 8dd, J6.1,
14.6 Hz, 1H), 4.36 8dd, J5.6, 14.6 Hz, 1H), 3.71 8s, 3H),
3.00 8dd, J1.2, 15.6 Hz, 1H), 2.84 8d, J15.6 Hz, 1H),
2.52±2.35 8m, 3H), 2.21±2.13 8m, 1H); 13C NMR
8100 MHz, CDCl3): d 171.66, 170.39, 164.95, 137.45,
134.60, 134.50, 129.90 82£), 129.32, 129.10, 128.84 82£),
128.47, 128.26, 127.79, 94.04, 70.29, 51.74, 44.53, 26.24,
25.40, 24.65; Anal. calcd for C22H23NO6S: C, 61.52; H,
5.40. Found: C, 61.66; H, 5.49.
4.4.9. [R1t-Bu, R2Tol]: Methyl 5-t-butylcarbamoyl-2-
hydroxy-5-.4-methylphenylsulfonyl)-1-cyclohexene-1-
carboxylate. Mp150±1518C; IR 8CHCl3) 3430, 3033,
1743, 1668 cm21; ESI-MS: C20H28NO6S m/z 8%)340
8100), 410 8M111, 5); HRMS 8ESI, M111) calcd for
C20H28NO6S 410.1638, found 410.1646; 1H NMR 8400
MHz, CDCl3): d 12.04 8s, 1H), 7.70 8dd, J1.9, 8.1 Hz,
2H), 7.32 8d, J8.1 Hz, 2H), 6.55 8br s, 1H), 3.73 8s, 3H),
2.90 8d, J15.6 Hz, 1H), 2.74 8d, J15.6 Hz, 1H), 2.37 8s,
3H), 2.36±2.28 8m, 3H), 2.15±2.09 8m, 1H), 1.35 8br s, 9H);
13C NMR 8100 MHz, CDCl3): d 171.78, 170.01, 163.76,
145.77, 131.98, 130.00 82£), 129.69 82£), 94.50, 70.56,
51.71, 51.95, 28.32 83£), 26.12, 25.23, 24.95, 21.70; Anal.
calcd for C20H27NO6S: C, 58.66; H, 6.65. Found: C, 58.78;
H, 6.84.
4.4.5. [R1Bn, R2Me]: 1-Benzyl-3-.4-methylsulfonyl)-
2,6-azinanedione. Viscous oil; IR 8CHCl3) 1741,
1661 cm21; ESI-MS: C13H16NO4S m/z 8%)91 8100), 154
891), 282 8M111, 95); HRMS 8ESI, M111) calcd for
C13H16NO4S 282.0801, found 282.0800; 1H NMR
8400 MHz, CDCl3): d 7.32±7.21 8m, 5H), 5.04 8d, J
14.1 Hz, 1H), 4.96 8d, J14.1 Hz, 1H), 4.01 8t, J5.5 Hz,
1H), 3.16 8s, 3H), 3.15±3.08 8m, 1H), 2.74±2.67 8m, 2H),
2.37±2.29 8m, 1H); 13C NMR 8100 MHz, CDCl3): d 170.44,
165.80, 136.21, 128.85, 128.53 83£), 127.67, 63.83, 43.63,
41.98, 29.46, 16.16; Anal. calcd for C13H15NO4S: C, 55.50;
H, 5.37. Found: C, 55.58; H, 5.48.
4.4.10. [R1t-Bu, R2Ph]: Methyl 5-t-butylcarbamoyl-2-
hydroxy-5-.4-phenylsulfonyl)-1-cyclohexene-1-carboxyl-
ate. Mp139±1408C; IR 8CHCl3) 3440, 3041, 1744,
1673 cm21; ESI-MS: C19H26NO6S m/z 8%)58 878), 166
849), 254 878), 308 875), 396 8M111, 100); HRMS 8ESI,
M111) calcd for C19H26NO6S 396.1482, found 396.1482;
1H NMR 8400 MHz, CDCl3): d 12.04 8s, 1H), 7.84 8dd,
J1.9, 8.1 Hz, 2H), 7.69±7.65 8m, 1H), 7.56±7.52 8m,
2H), 6.53 8br s, 1H), 3.73 8s, 3H), 2.92 8dd, J2.2,
15.6 Hz, 1H), 2.75 8d, J15.6 Hz, 1H), 2.43±2.34 8m,
3H), 2.23±2.18 8m, 1H), 1.35 8br s, 9H); 13C NMR 8100
MHz, CDCl3): d 171.75, 170.00, 163.60, 135.06, 134.59,
130.08 82£), 129.25 82£), 94.43, 70.63, 51.99, 51.73, 28.40
83£), 26.10, 25.34, 24.94; Anal. calcd for C19H25NO6S: C,
57.70; H, 6.37. Found: C, 57.82; H, 6.52.
4.4.6. [R1Bn, R2n-Bu]: 1-Benzyl-3-.4-n-butylsulfo-
nyl)-2,6-azinanedione. Mp66±678C; IR 8CHCl3) 1743,
1672 cm21; ESI-MS: C16H22NO4S m/z 8%)91 8100), 202
815), 324 8M111, 64); HRMS 8ESI, M111) calcd for
C16H22NO4S 324.1271, found 324.1275; 1H NMR 8400
MHz, CDCl3): d 7.32±7.23 8m, 5H), 5.03 8d, J14.1 Hz,
1H), 4.96 8d, J14.1 Hz, 1H), 4.01 8br s, 1H), 3.32±3.25 8m,
2H), 3.16±3.08 8m, 1H), 2.74±2.68 8m, 2H), 2.35±2.25 8m,
1H), 1.82 8m, 2H), 1.51±1.41 8m, 2H), 0.95 8t, J7.4 Hz,
3H); 13C NMR 8100 MHz, CDCl3): d 170.60, 165.95,
136.29, 128.50, 128.32 82£), 127.60 82£), 61.80, 53.58,
43.59, 29.51, 23.79, 21.61, 16.21, 13.49; Anal. calcd for
C16H21NO4S: C, 59.42; H, 6.54. Found: C, 59.56; H, 6.67.
4.4.7. [R1Tryptaminyl, R2Tol]: 1-{2-.1H-benzo[b]-
azol-3-yl)ethyl}-3-.4-methylphenylsulfonyl)-2,6-azinane-
4.4.11. [R1t-Bu, R2Me]: Methyl 5-t-butylcarbamoyl-
2-hydroxy-5-.4-methylsulfonyl)-1-cyclohexene-1-carb-
oxylate. Mp141±1428C; IR 8CHCl3) 3436, 3031, 1738,
1667 cm21; ESI-MS: C14H24NO6S m/z 8%)58 869), 149
8100), 246 842), 334 8M111, 36); HRMS 8ESI, M111)
calcd for C14H24NO6S 334.1325, found 334.1324; 1H
NMR 8400 MHz, CDCl3): d 12.07 8s, 1H), 6.33 8br s, 1H),
3.76 8s, 3H), 3.08 8dd, J2.3, 15.6 Hz, 1H), 2.88 8s, 3H),
2.78 8dt, J1.7, 15.6 Hz, 1H), 2.47±2.44 8m, 2H), 2.40±
2.34 8m, 1H), 2.23±2.15 8m, 1H), 1.32 8br s, 9H); 13C
NMR 8100 MHz, CDCl3): d 171.67, 169.92, 164.66,
94.14, 69.55, 52.18, 51.77, 36.66, 28.22 83£), 25.87,
24.41, 23.66; Anal. calcd for C14H23NO6S: C, 50.43; H,
6.95. Found: C, 50.37; H, 6.88.
dione. Mp177±1798C; IR 8CHCl3) 3025, 1667 cm21
;
ESI-MS: C22H23N2O4S m/z 8%)411 8M111, 100);
HRMS 8EI, M1) calcd for C22H22N2O4S 410.1302, found
410.1305; H NMR 8300 MHz, CDCl3): d 8.07 8br s, 1H),
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7.72 8d, J8.4 Hz, 2H), 7.70 8d, J6.3 Hz, 1H), 7.36 8d,
J8.4 Hz, 2H), 7.33 8d, J7.8 Hz, 1H), 7.18±7.11 8m, 2H),
7.02 8d, J2.4 Hz, 1H), 4.11±4.02 8m, 3H), 3.28±3.15 8m,
1H), 2.98 8t, J7.8 Hz, 2H), 2.75±2.60 8m, 2H), 2.45 8s,
3H), 2.23±2.15 8m, 1H); 13C NMR 875 MHz, CDCl3): d
170.64, 164.77, 145.73, 136.05, 134.84, 129.84 82£),
128.97 82£), 127.46, 122.33, 121.93, 119.33, 118.87,
112.28, 111.06, 65.64, 40.95, 29.25, 23.31, 21.77, 17.55.
4.4.8. Methyl 5-{2-.1H-benzo[b]azol-3-yl)ethylcarba-
moyl}-2-hydroxy-5-.4-methylphenylsulfonyl)-1-cyclo-
hexene-1-carboxylate. Viscous oil; IR 8CHCl3) 3452,
1652 cm21; ESI-MS: C26H29N2O6S m/z 8%)497 8M111,
100); HRMS 8EI, M1) calcd for C26H28N2O6S 496.1670,
4.4.12. [R1t-Bu, R2n-Bu]: Methyl 5-t-butylcarbamoyl-
2-hydroxy-5-.4-n-butylsulfonyl)-1-cyclohexene-1-carb-
oxylate. Mp88±898C; IR 8CHCl3) 3448, 3024, 1731,
1679 cm21; ESI-MS: C17H30NO6S m/z 8%)58 845), 166