Singh et al.
mixture was concentrated on a rotatory evaporator at room
temperature, and the crude product was purified by column
chromatography over 60-120 mesh silica gel using 0.5% ethyl
acetate-hexane as eluent to furnish 1.95 g (63% yield) of 9a as a
colorless oil.
3.4 Hz), 5.27 and 5.68 (2 × s, 2H), 7.29-7.50 (m, 4H), 7.76-
7.86 (m, 2H), 8.00 (m, 1H); 13C NMR (50 MHz, CDCl3) δ 24.3,
34.9, 36.4, 37.7, 62.4, 86.6, 118.2, 118.4, 125.6, 126.0, 126.2, 126.3,
126.5, 128.2, 128.6, 131.9, 134.1, 138.9, 146.6; MS (m/z) 311 (M
+ H)+; HRMS Calcd for C20H22O3: 310.1569. Found: 310.1547.
9-(1-Phenyl-vinyl)-7,8,12-trioxaspiro[5.6] Dodecane (10a). Yield
52%, oil; 1H NMR (200 MHz, CDCl3) δ 1.40-2.16 (m, 12H), 3.75
(td, 1H, J ) 12.3, 3.3 Hz), 4.03 (dt, 1H, J ) 12.3, 1.0 Hz), 5.04
(dd, 1H, J ) 11.2, 3.4 Hz), 5.35 and 5.41 (2 × s, 2H), 7.29-7.41
(m, 5H); 13C NMR (50 MHz, CDCl3) δ 23.1, 23.5, 25.8, 32.0, 34.6,
37.8, 60.7, 85.8, 107.0, 116.2, 127.1, 128.1, 128.8, 140.1, 146.8;
MS (m/z) 275 (M + H)+; Anal. Calcd for C17H22O3 + 0.1H2O: C,
73.93; H, 8.10. Found: C, 74.63; H, 8.58.
3,3-Dimethyl-7-(1-phenyl-vinyl)-[1,2,4] Trioxepane (8a). Yield
1
64%, oil; H NMR (200 MHz, CDCl3) δ 1.30 (s, 3H), 1.51 (s,
3H), 1.80-1.87 (m, 1H), 2.09 (m, 1H,) 3.76 (td, 1H, J ) 12.3, 3.3
Hz), 4.02 (t, 1H, J ) 12.3 Hz), 5.06 (dd, 1H, J ) 11.2, 3.2 Hz),
5.36 & 5.43 (2 × s, 2H), 7.27-7.44 (m, 5H); 13C NMR (50 MHz,
CDCl3) δ 22.4, 25.3, 37.4, 61.0, 85.7, 106.9, 116.2, 127.0, 128.2,
128.8, 140.1, 146.5; MS (m/z) 235 (M + H)+; HRMS Calcd. for
C14H18O3: 234.1256. Found: 234.1240.
7-[1-(4-Chloro-phenyl)-vinyl]-3,3-dimethyl-[1,2,4] Trioxepane
(8b). Yield 51%, mp 41-42 °C; H NMR (200 MHz, CDCl3) δ
9-[1-(4-Chloro-phenyl)-vinyl]-7,8,12-trioxa-spiro[5.6] Dode-
cane (10b). Yield 48%, oil; 1H NMR (200 MHz, CDCl3) δ 1.42-
2.16 (m, 12H), 3.76 (td, 1H, J ) 12.3, 3.1 Hz), 4.03 (t, 1H, J )
12.3 Hz), 5.00 (dd, 1H, J ) 11.2, 3.2 Hz), 5.38 and 5.42 (2 × s,
2H), 7.31-7.37 (m, 4H); 13C NMR (50 MHz, CDCl3) δ 23.1, 23.5,
25.8, 31.9, 34.6, 37.5, 60.6, 85.8, 107.1, 117.1, 128.5, 128.9, 134.1,
138.5, 145.5; MS (m/z) 309 (M + H)+; Anal. Calcd for C17H21O3-
Cl + 0.1 H2O: C, 65.73; H, 6.88. Found: C, 65.57; H, 6.89.
9-(1-Biphenyl-4-yl-vinyl)-7,8,12-trioxa-spiro[5.6] Dodecane
1
1.30 (s, 3H), 1.49 (s, 3H), 1.78-1.85 (m, 1H), 2.04-2.16 (m, 1H),
3.76 (td, 1H, J ) 12.4, 3.2 Hz), 4.02 (t, 1H, J ) 12.4 Hz), 5.00
(dd, 1H, J ) 11.2, 2.8 Hz), 5.38 and 5.43 (2 × s, 2H), 7.27-7.41
(m, 4H); 13C NMR (50 MHz, CDCl3) δ 22.4, 25.3, 37.1, 60.9, 85.6,
106.9, 117.0, 128.4, 128.9, 134.1, 138.4, 145.3; MS (m/z) 295, 297
(M + H)+; Anal. Calcd for C14H17O3Cl + 0.2H2O: C, 61.74; H,
6.43. Found: C, 61.43; H, 6.79.
1
7-(1-Biphenyl-4-yl-vinyl)-3,3-dimethyl-[1,2,4] Trioxepane (8c).
Yield 46%, mp 81-84 °C; 1H NMR (200 MHz, CDCl3) δ 1.31 (s,
3H), 1.53 (s, 3H), 1.84-1.92 (m, 1H), 2.14 (m, 1H,), 3.78 (td, 1H,
J ) 12.4, 3.4 Hz), 4.05 (t, 1H, J ) 12.4 Hz), 5.11 (dd, 1H, J )
(10c). Yield 43%, mp 83-86 °C; H NMR (200 MHz, CDCl3) δ
1.43-2.14 (m, 12H), 3.78 (td, 1H, J ) 12.3, 3.3 Hz), 4.06 (t, 1H,
J ) 12.3 Hz), 5.09 (dd, 1H, J ) 11.2, 3.3 Hz), 5.39 and 5.49 (2 ×
s, 2H), 7.33-7.62 (m, 9H); 13C NMR (50 MHz, CDCl3) δ 23.2,
23.5, 25.8, 32.0, 34.6, 37.8, 60.6, 85.8, 107.1, 116.2, 127.4, 127.5,
127.8, 129.2, 138.9, 141.0, 146.2; MS (m/z) 351 (M + H)+; Anal.
Calcd for C23H26O3: C, 78.82; H, 7.47. Found: C, 78.69; H, 7.76.
9-(1-Naphthyl-vinyl)-7,8,12-trioxa-spiro[5.6] Dodecane (10d).
11.2, 3.3 Hz), 5.39 and 5.50 (2 × s, 2H), 7.33-7.61 (m, 9H); 13
C
NMR (50 MHz, CDCl3) δ 22.5, 25.4, 37.4, 61.1, 85.6, 106.9, 116.2,
127.4, 127.5, 127.8, 129.2, 138.9, 141.1, 146.0; MS (m/z) 310 M+;
HRMS Calcd for C20H22O3: 310.1569. Found: 310.1580.
3,3-Dimethyl-7-(1-naphthyl-vinyl)-[1,2,4] Trioxepane (8d).
1
Yield 44%, oil; H NMR (200 MHz, CDCl3) δ 1.42-1.62 (m, 10
1
Yield 66%, oil; H NMR (200 MHz, CDCl3) δ 1.26 (s, 3H), 1.53
H), 1.73-1.97 (m, 2H) 3.67 (td, 1H, J ) 12.4, 3.4 Hz), 3.91 (dt,
1H, J ) 12.3, 1.3 Hz), 4.94 (dd, 1H, J ) 10.8, 3.1 Hz), 5.27 and
5.67 (2 × s, 2H), 7.28-7.50 (m, 4H), 7.76-7.86 (m, 2H), 8.00-
8.05 (m, 1H); 13C NMR (50 MHz, CDCl3) δ 23.1, 23.4, 25.8, 31.9,
34.5, 38.1, 60.6, 86.6, 107.0, 118.3, 125.6, 126.2, 126.3,126.5,
128.2, 128.6, 134.1, 138.9, 146.6; MS (m/z) 324 M+; HRMS Calcd
for C21H24O3: 324.1726. Found: 324.1721.
(s, 3H), 1.76-1.86 (m, 1H), 1.93-2.13 (m, 1H,), 3.67 (td, 1H, J
) 12.4, 3.4 Hz), 3.89 (dt, 1H, J ) 12.3, 1.3 Hz), 4.95 (dd, 1H, J
) 11.0, 3.3 Hz), 5.28 and 5.68 (2 × s, 2H), 7.28-7.50 (m, 4H),
7.77-7.87 (m, 2H), 7.99-8.02 (m, 1H); 13C NMR (50 MHz,
CDCl3) δ 22.5, 25.2, 37.8, 60.9, 86.6, 106.9, 118.4, 125.6, 126.1,
126.2, 126.3, 126.6, 128.3, 128.7, 131.9, 134.1, 138.9, 146.6; MS
(m/z) 284 M+; HRMS Calcd. for C18H20O3: 284.1413. Found:
284.1417.
8-(1-Phenyl-vinyl)-6,7,11-trioxa-spiro[4.6] Undecane (9a). Yield
63%, oil; 1H NMR (200 MHz, CDCl3) δ 1.62-1.91 (m, 8H), 2.06-
2.21 (m, 2H), 3.81 (td, 1H, J ) 12.2, 3.5 Hz), 3.97 (dt, 1H, J )
12.2, 1.3 Hz), 5.11 (dd, 1H, J ) 11.0, 3.5 Hz), 5.36 and 5.42 (2 ×
s, 2H), 7.25-7.43 (m, 5H); 13C NMR (50 MHz, CDCl3) δ 24.3,
34.9, 36.4, 37.4, 62.4, 85.8, 116.2, 118.4, 127.1, 128.1, 128.8, 140.1,
146.6; MS (m/z) 261 (M + H)+; Anal. Calcd. for C16H20O3: C,
73.81; H, 7.74. Found: C, 73.93; H, 7.94.
2-(8-Hydroperoxy-cyclooct-1-enyl)ethanol) (13). A solution of
homoallylic alcohol 12 (3.2 g) and methylene blue (75 mg) in
acetonitrile (300 mL) was irradiated with a 500 W tungsten-
halogen lamp at -10 °C, while a slow stream of O2 was bubbled
into the reaction mixture. After 3 h, the reaction mixture was
concentrated under vacuum at room temperature, and the crude
product was purified by column chromatography over 60-120 mesh
silica gel (deactivated with 12% v/w of water) using 25% ethyl
acetate-hexane as eluent to furnish 2.59 g (67% yield) of
δ-hydroxyhydroperoxide 13 as a colorless oil; 1H NMR (200 MHz,
CDCl3) δ 1.28-1.80 (m, 6H), 2.11-2.18 (m, 4H), 2.40-2.42 (m,
2H) 3.79 (td, 1H, J ) 10.0, 3.4 Hz), 3.99-4.10 (m, 1H), 5.16 (dd,
1H, J ) 12.0, 4.6 Hz), 5.78 (t, 1H, J ) 8.4 Hz); 13C NMR (50
MHz, CDCl3) δ 24.6, 27.2, 27.8, 30.9, 31.8, 64.6, 83.9, 130.9,
138.5; MS (m/z) 169 (M + H - H2O)+.
General Procedure for the Preparation of 1,2,4-Trioxocanes
from δ-Hydroxyhydroperoxide (Preparation of 17 as Repre-
sentative). A solution of δ-hydroxyhydroperoxide 13 (2.0 g),
cyclopentanone (2.4 mL, 2.5 equiv), and conc HCl (0.5 mL) in
dichloromethane (50 mL) was stirred for 1 h at room temperature.
The reaction mixture was concentrated on a rotatory evaporator at
room temperature, and the crude product was purified by column
chromatography over 60-120 mesh silica gel using 0.5% ethyl
acetate-hexane as eluent to furnish 1.12 g (41% yield) of 17 as a
colorless oil, 1H NMR (200 MHz, CDCl3) δ 1.33-1.72 (m, 16H),
2.10 (dd, 2H, J ) 14.2, 5.4 Hz), 2.17-2.43 (m, 2H), 3.40 (t, 1H,
J ) 10.0 Hz), 3.87 (ddd, 1H, J ) 12.1, 5.5, 1.6 Hz), 5.18 (dd, 1H,
J ) 11.3, 4.1 Hz), 5.53 (t, 1H, J ) 8.3 Hz); 13C NMR (50 MHz,
CDCl3) δ 24.2, 24.4, 24.7, 27.2, 27.6, 30.9, 34.0, 35.9, 36.8, 66.4,
80.6, 116.1, 128.5, 143.1; MS (m/z) 253 (M + H)+; HRMS Calcd
for C15H24O3: 252.17255. Found: 252.17254.
8-[1-(4-Chloro-phenyl)-vinyl]-6,7,11-trioxa-spiro[4.6] Unde-
1
cane (9b). Yield 48%, oil; H NMR (200 MHz, CDCl3) δ 1.68-
1.89 (m, 8H), 2.03-2.21 (m, 2H), 3.82 (td, 1H, J ) 12.1, 3.5 Hz),
3.97 (dt, 1H, J ) 12.1, 1.3 Hz), 5.06 (dd, 1H, J ) 11.0, 3.2 Hz),
5.39 and 5.43 (2 × s, 2H), 7.27-7.46 (m, 4H); 13C NMR (50 MHz,
CDCl3) δ 24.4, 34.8, 36.4, 37.0, 62.3, 85.6, 116.9, 118.4, 128.5,
128.9, 134.1, 138.4, 145.4; MS (m/z) 295, 297 (M + H)+; HRMS
Calcd for C16H19O3Cl: 294.1023. Found: 294.1044.
8-(1-Biphenyl-4-yl-vinyl)-6,7,11-trioxa-spiro[4.6] Undecane
1
(9c). Yield 35%, mp 73-75 °C; H NMR (200 MHz, CDCl3) δ
1.71-1.75 (m, 8H), 1.88-1.95 (m, 1H), 2.08-2.24 (m, 1H), 3.85
(td, 1H, J ) 12.3, 3.5 Hz), 4.00 (t, 1H, J ) 12.3 Hz), 5.15 (dd, 1H,
J ) 11.2, 3.6 Hz), 5.40-5.50 (2 × s, 2H), 7.34-7.61 (m, 9H); 13
C
NMR (50 MHz, CDCl3) δ 24.4, 34.9, 36.5, 37.3, 62.4, 85.7, 116.2,
118.5, 127.4, 127.5, 127.8, 129.2, 138.9, 141.0, 146.2; MS (m/z)
337 (M + H)+; Anal. Calcd for C22H24O3: C, 78.54; H, 7.19.
Found: C, 78.28; H, 7.26.
8-(1-Naphthyl-vinyl)-6,7,11-trioxa-spiro[4.6] Undecane (9d).
Yield 38%, oil; 1H NMR (200 MHz, CDCl3) δ 1.68-1.79 (m, 7H),
1.86-1.87 (m, 1H) 2.02-2.16 (m, 2H), 3.72 (td, 1H, J ) 12.1,
3.6 Hz), 3.84 (dt, 1H, J ) 12.1, 1.5 Hz), 5.00 (dd, 1H, J ) 10.8,
9060 J. Org. Chem., Vol. 71, No. 24, 2006