J. H. Rigby et al. / Tetrahedron 56 (2000) 10101±10111
10109
one (11). From the acyl azide (46 mg, 0.2 mmol) in 4.0 mL
of benzene and 3 (1.0 mL, 0.5 mmol) was obtained 45 mg
(52%) of the desired produce as a colorless oil after ¯ash
chromatography (3.5:1 hexanes/EtOAc12% NEt3): 1H
NMR (CDCl3, 400 MHz) d 6.48 (s, 1H), 5.70 (t,
J4.0 Hz, 1H), 4.07±3.86 (m, 5H), 3.28±3.18 (m, 1H),
3.15±2.92 (m, 4H), 2.74±2.43 (m, 4H), 2.34 (d,
J5.6 Hz, 1H), 2.18±2.07 (m, 2H), 1.86±1.72 (m, 3H),
1.40 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 170.3, 137.6,
107.5, 102.1, 64.4, 63.7, 58.1, 56.8, 46.5, 35.7, 34.8, 32.3,
32.1, 27.2, 26.6, 25.1, 24.6, 22.9; IR (neat) n 2964, 2929,
2896, 1723, 1687 cm21; mass spectrum (EI) m/e (rel. int.)
431 (M1, 7.2), 312 (47.4), 119 (100); HRMS calcd for
C18H25NO3S4 431.0717, found 431.0712.
2.65 (m, 8H), 2.30±1.68 (m, 8H); 13C NMR (CDCl3,
100 MHz) d 172.5, 140.9, 134.5, 130.9, 130.0, 128.1,
128.0, 127.8, 94.8, 62.6, 59.1, 57.0, 39.2, 39.1, 33.3, 33.1,
31.7, 31.1, 29.9, 28.9, 28.2, 28.0, 27.7, 27.4; IR (neat) n
2918, 1712, 1650, 1326 cm21; mass spectrum (EI) m/e (rel.
int.) 423 (M1, 17.8), 289 (21.0), 132 (100), 120 (84.7), 87
(51.7); HRMS calcd for C20H24NOS4 423.0819, found
423.0817.
2-Aza-2-(1,3-dithiepan-2-yl)-4-methyl-3-methylene-6,11-
dithiaspiro[4.6]undecan-1-one (15). From the acyl azide
(31 mg, 0.25 mmol) in 5.0 mL of benzene and 4 (1.0 mL,
0.5 mmol) was obtained 41 mg (50%) of the desired product
as a colorless oil after ¯ash chromatography (15:1 hexanes/
EtOAc12% NEt3). Due to the coexistence of several
conformers of the two 7-membered rings at room tempera-
ture, the peaks of each conformer could be observed by both
1H NMR and 13C NMR: 1H NMR (CDCl3, 400 MHz) d 6.47
(s, 1H), 5.20 (s, 0.5H), 5.06 (t, J2.2 Hz, 1H), 4.91 (d, 0.5H,
J2.8 Hz), 4.52 (t, J2.2 Hz, 1H), 3.34±3.07 (m, 1H),
3.01±2.58 (m, 8H), 2.22±1.71 (m, 8H), 1.34 (d,
J6.8 Hz, 3H), 1.29 (d, 0.5H, J6.4 Hz); 13C NMR
(CDCl3, 100 MHz) d 172.6, 143.1, 91.9, 61.7, 58.8, 45.6,
39.3, 39.1, 33.1 32.9, 31.8, 31.6, 31.5, 30.4, 30.0, 29.7, 28.9,
28.2, 27.7, 27.4, 27.3, 27.2; IR (neat) 2923, 2850, 1713,
1649, 1326, 1213 cm21; mass spectrum (EI) m/e (rel. int.)
361 (M1, 55.6) 228 (53.3), 133 (100), 87 (50.2); HRMS
calcd for C15H23NOS4 361.0663, found 361.0661.
2-Aza-2-(1,3-dithian-2-yl)-3-methyl-4-phenyl-6,10-di-
thiaspiro[4.5]decan-1-one (12). From the acyl azide
(38 mg, 0.2 mmol) in 4.0 mL of benzene and 3 (1.0 mL,
0.5 mmol) was obtained 67 mg (85%) of the desired product
as a colorless oil after ¯ash chromatography (5:1 hexanes/
1
EtOAc12% NEt3). H NMR (CDCl3, 400 MHz) d 7.38±
7.29 (m, 5H), 6.67 (s, 1H), 5.47 (t, J2.2 Hz, 1H), 4.42 (t,
J2.2 Hz, 1H), 3.97 (t, J1.8 Hz, 1H), 3.82 (dt,
J113.4 Hz, J22.4 Hz, 1H), 3.66 (dt, J113.4 Hz,
J22.4 Hz, 1), 3.23±3.10 (m, 2H), 3.08±2.96 (m, 2H),
2.60 (td, J114.0 Hz, J23.4 Hz, 1H), 2.51 (td,
J114.0 Hz, J23.4 Hz, 1H), 2.21±2.06 (m, 2H), 1.91±
1.69 (m, 2H); 13C NMR (CDCl3, 100 MHz) d 170.4,
141.9, 134.6, 130.1, 128.4, 128.0, 94.1, 57.1, 55.6, 50.7,
32.5, 32.4, 27.9, 27.1, 25.1, 24.0; IR (neat) n 2918, 1710,
1645, 1354, 1210 cm21; mass spectrum (EI) m/e (rel. int.)
395 (M1, 7.7) 276 (86.6), 119 (100); HRMS calcd for
C18H21NOS4 395.0506, found 395.0505.
7-(1,3-Dithian-2-yl)spiro[1,3-dithiane-2,30-3,40,50,60,70-
pentahydroindole]-8-one (16). At room temperature, a
total of 54 mg (0.15 mmol) of 10 was dissolved into
0.5 mL of CDCl3 (obtained from Cambridge Isotope
Laboratories, Inc.; directly used without passing through
basic alumina) in a NMR tube. The reaction turned out to
2-Aza-2-(1,3-dithian-2-yl)-4-methyl-3-methylene-6,10-
dithiaspiro[4.5]decan-1-one (13). From the acyl azide
(25 mg, 0.2 mmol) in 4.0 mL of benzene and 3 (1.0 mL,
0.5 mmol) was obtained 52 mg (78%) of the desired product
as a colorless oil after ¯ash chromatography (7:1 hexanes/
1
be a slow process and monitored by H NMR. After 2 d at
room temperature, the ratio between the desired product and
the starting material was 13.5:1. This ratio had been the
same even after 7 d: H NMR (CDCl3, 400 MHz) d 6.45
1
1
EtOAc12% NEt3). H NMR (CDCl3, 400 MHz) d 6.53 (s,
(s, 1H), 3.90 (dt, J113.6 Hz, J22.4 Hz, 2H), 3.08 (dt,
J113.6 Hz, J22.4 Hz, 2H), 2.96 (td, J113.6 Hz,
J23.6 Hz, 2H), 2.76±2.68 (m, 2H), 2.54 (td, J113.6 Hz,
1H), 5.30 (t, J2.4 Hz, 1H), 4.46 (t, J2.4 Hz, 1H), 3.99
(dt, J113.4 Hz, J22.4 Hz, 1H), 3.54±3.43 (m, 1H), 3.17±
3.04 (m, 2H), 3.04±2.92 (m, 2H), 2.82±2.73 (m, 1H), 2.69±
2.54 (m, 2H), 2.28±2.06 (m, 2H), 1.92±1.74 (m, 2H), 1.31
(d, J7.2 Hz, 3H): 13C NMR (CDCl3, 100 MHz) d 170.9,
143.7, 91.2, 56.9, 50.9, 43.7, 32.5, 32.4, 27.3, 26.3, 25.1,
J23.6 Hz, 2H), 2.25±2.05 (m, 4H), 1.98±1.64 (m, 6H); 13
C
NMR (CDCl3, 100 MHz) d 175.8, 138.2, 114.4, 55.7, 49.1,
32.8, 24.9, 24.2, 230, 22.2, 21.9, 19.8. After the solvent was
removed, a total of 54 mg (93% of the desired product based
on the ratio) of an inseparable mixture was obtained as a
24.6, 11.6; IR (neat) n 2910, 1710, 1680, 1340, 1300 cm21
;
mass spectrum (EI) m/e (rel. int.) 333 (M1, 5.7), 214 (99.5),
119 (100); HRMS calcd for C13H19NOS4 333.0350, found
333.0350.
pale yellow oil. IR (neat) n 2933, 1705, 1668, 1315 cm21
;
mass spectrum (EI) m/e (rel. int.) 359 (M1, 8.0), 240 (50.6),
119 (100); HRMS calcd for C15H21NOS4 359.0506, found
359.0506.
2-Aza-2-(1,3-diethiepan-2-yl)-3-methylene-4-phenyl-6,11-
dithiaspiro[4.6]undecan-1-one (14). From the acyl azide
(38 mg, 0.2 mmol) in 4.0 mL of benzene and oxadiazoline 4
(1.0 mL, 0.5 mmol) was obtained 47 mg (56%) of the
desired product as a colorless oil after ¯ash chromatography
(10:1 hexanes/EtOAc12% NEt3). Due to the coexistence of
several conformers of the two 7-membered rings at room
temperature, the peaks of each conformer could be observed
by both 1H NMR and 13C NMR: 1H NMR (CDCl3,
400 MHz) d 7.48±7.30 (m, 5H), 6.58 (br s, 1H), 5.19 (s,
1H), 5.15 (br s, 0.5H), 4.47 (t, J2.0 Hz, 1H), 4.42 (m,
0.5H), 4.17 (t, J2.0 Hz, 1H), 3.35±3.26 (m, 1H), 2.93±
2-Aza-2-(1,3-dithian-2-yl)-3-methyl-4-phenyl-6,10-di-
thiaspiro[4.5]dec-3-en-1-one (17). At room temperature,
60 mg (0.15 mmol) of 12 was dissolved in 0.5 mL of
CDCl3 (obtained from Cambridge Isotope Laboratories,
Inc.; directly used without passing through basic alumina)
in a NMR tube: 1H NMR demonstrated that the reaction was
1
complete. H NMR (CDCl3, 400 MHz) d 7.44±7.30 (m,
5H), 6.59 (s, 1H), 3.95 (dt, J113.6 Hz, J22.4 Hz, 2H),
3.17±3.08 (m, 2H), 3.00 (td, J114.0 Hz, J23.8 Hz, 2H),
2.51 (td, J114.0 Hz, J23.8 Hz, 2H), 2.33 (s, 3H), 2.18±
2.10 (m, 2H), 1.91±1.74 (m, 2H); 13C NMR (CDCl3,