4996 J . Org. Chem., Vol. 62, No. 15, 1997
Kita et al.
product on TLC (hexane/ethyl acetate ) 5/1): Rf ) 0.1); IR
166.7, 216.7; HRMS m/z Calcd for C17H20O3 (M+): 272.1412.
Found: 272.1409.
1
3500, 2863, 1710 cm-1; H NMR δ 1.50-2.60 (m, 12H), 5.44
(dd, 1H, J ) 7.0, 10.0 Hz), 7.45 (t, 2H, J ) 7.5 Hz), 7.57 (t,
1H, J ) 7.5 Hz), 8.03 (d, 2H, J ) 7.5 Hz). 4; triol monoben-
zoate (less polar product on TLC (hexane/ethyl acetate ) 5/1):
Rf ) 0.2); IR 3400, 2865, 1700 cm-1; 1H NMR δ 1.50-2.30 (m,
11H), 2.90-3.10 (m, 1H), 4.60 (t, 1H, J ) 8.5 Hz), 7.46 (t, 2H,
J ) 7.5 Hz), 7.60 (t, 1H, J ) 7.5 Hz), 8.02 (d, 2H, J ) 7.5 Hz).
2-Acetoxy-1-oxosp ir o[4.4]n on a n e (2b). cis-1b (30 mg,
0.153 mmol) and BF3‚OEt2 (19 µL, 0.153 mmol) gave 2b as a
2-(Ben zoyloxy)-1-oxosp ir o[4.6]u n d eca n e (17). 12 (122.3
mg, 0.427 mmol) and BF3‚OEt2 (57 µL, 0.427 mmol) gave 17
as a colorless oil (67.1 mg, 55%): IR 2921, 2855, 1752, 1725
cm-1; 1H NMR δ 1.25-2.18 (m, 15H), 2.35-2.55 (m, 1H), 5.43
(dd, 1H, J ) 8.5, 11.0 Hz), 7.42 (t, 2H, J ) 7.5 Hz), 7.55 (t,
1H, J ) 7.5 Hz), 8.06 (d, 2H, J ) 7.5 Hz); 13C NMR δ 23.3,
23.4, 25.6, 29.7, 31.8, 35.6, 37.2, 49.6 (spiro carbon), 75.6, 128.3,
129.5, 129.9, 133.2, 165.8, 216.4; HRMS m/z Calcd for C18H22O3
(M+): 286.1569. Found: 286.1542.
1
colorless oil (21.3 mg, 71%): IR 2955, 1742 cm-1; H NMR δ
1.50-2.00 (m, 11H), 2.14 (s, 3H), 2.36-2.55 (m, 1H), 5.15 (t,
1H, J ) 10.5 Hz); 13C NMR δ 20.7, 25.5, 25.7, 26.4, 32.9, 37.5,
38.6, 54.2 (spiro carbon), 75.5, 170.2, 217.2. Anal. Calcd for
C11H16O3: C, 67.33; H, 8.21. Found: C, 67.34; H, 8.19.
2-[(p-Nitr oben zoyl)oxy]-1-oxospir o[4.4]n on an e (2c). cis-
1c (1.0 g, 3.3 mmol) and BF3‚OEt2 (0.41 mL, 3.3 mmol) gave
2c as colorless crystals (793 mg, 79%): mp 108-109 °C (CH2-
Cl2/hexane); IR 2955, 2869, 1750, 1730 cm-1; 1H NMR δ 1.20-
2.20 (m, 11H), 2.40-2.60 (m, 1H), 5.43 (dd, 1H, J ) 8.5, 10.0
Hz), 8.24 (d, 2H, J ) 8.5 Hz), 8.30 (d, 2H, J ) 8.5 Hz); 13C
NMR δ 25.8, 26.0, 26.7, 33.2, 37.9, 39.0, 54.5 (spiro carbon),
77.0, 123.8, 131.3, 135.2, 150.9, 164.2, 216.6. Anal. Calcd for
C16H17NO5: C, 63.36; H, 5.65; N, 4.62. Found: C, 63.31; H,
5.63, N, 4.62.
3-Meth yl-2-oxocyclop en t-1-yl Ben zoa te (22a ). 19a (183
mg, 0.887 mmol) and BF3‚OEt2 (0.109 mL, 0.887 mmol) gave
22a as a colorless oil (149 mg, 81%): IR 2936, 2876, 1757, 1725
cm-1; 1H NMR δ 1.22 (d, 3H, J ) 7.5 Hz), 1.70-1.90 (m, 1H),
1.95-2.14 (m, 1H), 2.17-2.32 (m, 1H), 2.37-2.52 (m, 2H), 5.39
(dt, 1H, J ) 1.5, 8.5 Hz), 7.44 (t, 2H, J ) 7.5 Hz), 7.57 (t, 1H,
J ) 7.5 Hz), 8.39 (d, 2H, J ) 7.5 Hz); 13C NMR δ 15.7, 26.1,
26.4, 39.6, 76.5, 128.3, 129.8, 130.1, 133.2, 165.7, 214.3. Anal.
Calcd for C13H14O3: C, 71.54; H, 6.47. Found: C, 71.46; H,
6.44.
3-Meth yl-2-oxocyclop en t-1-yl p-Nitr oben zoa te (22b).
19b (448 mg, 1.69 mmol) and BF3‚OEt2 (0.214 mL, 1.69 mmol)
gave 22b as colorless needles (353 mg, 79%): m.p. 109-110
1
°C (MeOH); IR 2970, 2878, 1757, 1728 cm-1; H NMR δ 1.23
2-(Ca m p h a n oyloxy)-1-oxosp ir o[4.4]n on a n e (2d ). cis-1d
(60 mg, 0.180 mmol) and BF3‚OEt2 (22 µL, 0.180 mmol) gave
2d as a white solid (41.6 mg, 69%): mp 75.5-77 °C (hexane/
(d, 3H, J ) 7.5 Hz), 1.77-1.90 (m, 1H), 2.03-2.60 (m, 4H),
5.45 (dt, 1H, J ) 1.5, 9.0 Hz), 8.23 (d, 2H, J ) 8.5 Hz), 8.29 (d,
2H, J ) 8.5 Hz). Anal. Calcd for C13H13NO5: C, 59.30; H,
4.98; N, 5.34. Found: C, 59.10; H, 4.91; N, 5.32.
1
ethyl acetate); IR 2971, 1790, 1748 cm-1; H NMR δ 1.04 (s,
3H), 1.08 (s, 3H), 1.12 (s, 3H), 1.20-2.60 (m, 16H), 5.35 (dd,
1H, J ) 8.0, 10.0 Hz). Anal. Calcd for C19H26O5: C, 68.24; H,
7.84. Found: C, 67.90; H, 7.86.
3-Meth yl-2-oxo-3-p en tylcyclop en t-1-yl Ben zoa te (23a ).
20a (742 mg, 2.57 mmol) and BF3‚OEt2 (0.326 mL, 2.57 mmol)
gave 23a as a colorless oil (455 mg, 61%): IR 2930, 1755, 1725
1
cm-1; H NMR δ 0.88 (t, 3H, J ) 7.0 Hz), 1.14 (s, 3H), 1.19-
2-p-Tolu en esu lfon yl-1-oxosp ir o[4.4]n on a n e (7). cis-6
(38.8 mg, 0.126 mmol) and BF3‚OEt2 (20 µL, 0.126 mmol) gave
7 as a pale yellow powder (24.5 mg, 63%): mp 83-84 °C
1.52 (m, 8H), 1.80-2.02 (m, 3H), 2.42-2.52 (m, 1H), 5.36 (t,
1H, J ) 8.0 Hz), 7.44 (t, 2H, J ) 7.5 Hz), 7.57 (t, 1H, J ) 7.5
Hz), 8.08 (t, 2H, J ) 7.5 Hz); 13C NMR δ 14.3, 22.8, 23.6, 24.3,
25.7, 30.5, 32.5, 38.5, 46.8 (quaternary carbon), 76.9, 128.7,
129.8, 130.2, 133.6, 166.1, 216.5. Anal. Calcd for C18H24O3:
C, 74.97; H, 8.39. Found: C, 74.80; H, 8.39.
(hexane/ethyl acetate); IR 2870, 1754, 1368, 1176 cm-1 1H
;
NMR δ 1.20-2.10 (m, 11H), 2.30-2.50 (m, 1H), 2.45 (s, 3H),
4.77 (dd, 1H, J ) 8.5, 9.5 Hz), 7.34 (d, 2H, J ) 8.5 Hz), 7.85
(d, 2H, J ) 8.5 Hz); 13C NMR δ 21.7, 25.5, 25.7, 27.5, 32.6,
37.1, 38.6, 53.9 (spiro carbon), 80.1, 128.0, 129.8, 133.5, 144.9,
214.3; HRMS m/z Calcd for C16H20SO4 (M+): 308.1083.
Found: 308.1077.
2-p-Tolu en esu lfon yl-1-oxosp ir o[4.4]n on a n e (7). trans-6
(412 mg, 1.34 mmol) and BF3‚OEt2 (0.165 mL, 1.34 mmol) gave
7 (247 mg, 60%).
(1r,6r,7â)-1-Ch lor o-6-h ydr oxybicyclo[4.3.0]n on -7-yl ben -
zoa te (8): colorless oil: IR 3400, 1723, 1279 cm-1; 1H NMR δ
1.45-2.20 (m, 10H), 2.35-2.47 (m, 1H), 2.57-2.70 (m, 1H),
5.59 (dd, 1H, J ) 5.5, 9.0 Hz), 7.45 (t, 2H, J ) 7.5 Hz), 7.57 (t,
1H, J ) 7.5 Hz), 8.02 (d, 2H, J ) 7.5 Hz); HRMS m/z Calcd
for C9H13OCl (M+ - PhCOOH): 172.0655. Found: 172.0673.
2-(Ben zoyloxy)-7-ter t-bu tyl-1-oxospir o[4.4]n on an e (14).
9 (49.7 mg, 0.158 mmol) and BF3‚OEt2 (20 µL, 0.158 mmol)
gave 14 as a colorless oil (29.0 mg, 58%): IR 2957, 2867, 1752,
1725 cm-1; 1H NMR δ 0.87, 0.89 (each s, total 9H), 1.34-2.15
(m, 10H), 2.40-2.50 (m, 1H), 5.35, 5.38 (m, dd, total 1H, J )
8.5, 11.0 Hz), 7.44 (t, 2H, J ) 7.5 Hz), 7.56 (t, 1H, J ) 7.5 Hz),
8.07 (d, 2H, J ) 7.5 Hz). Anal. Calcd for C20H26O3: C, 76.40;
H, 8.33. Found: C, 76.40; H, 8.28.
3-Meth yl-2-oxo-3-pen tylcyclopen t-1-yl p-Nitr oben zoate
(23b). 20b (22.3 mg, 0.064 mmol) and BF3‚OEt2 (8 µL, 0.064
mmol) gave 23b as colorless crystals (16.2 mg, 73%): mp 59.5-
1
61 °C (hexane); IR 2960, 2930, 1755, 1730 cm-1; H NMR δ
0.89 (t, 3H, J ) 6.5 Hz), 1.15 (s, 3H), 1.12-1.58 (m, 8H), 1.85-
2.10 (m, 3H), 2.45-2.55 (m, 1H), 5.40 (t, 1H, J ) 10.0 Hz),
8.24 (d, 2H, J ) 8.5 Hz), 8.29 (d, 2H, J ) 8.5 Hz); 13C NMR δ
14.0, 22.5, 23.3, 24.0, 25.3, 30.3, 32.2, 38.2, 46.6 (quaternary
carbon), 77.4, 123.6, 131.1, 134.9, 150.8, 164.0, 215.6. Anal.
Calcd for C18H23NO5: C, 64.85; H, 6.95; N, 4.20. Found: C,
64.79; H, 6.90; N, 4.17.
3-Bu tyl-3-m eth yl-2-oxocycloh ex-1-yl Ben zoa te (24a )
and 2-Meth yl-2-(1-oxopen tyl)cyclopen t-1-yl Ben zoate (25a).
21a (42.7 mg, 0.148 mmol) and BF3‚OEt2 (18 µL, 0.148 mmol)
gave 24a (15.8 mg, 37%) and 25a (13.5 mg, 32%). 24a :
colorless oil; IR 2936, 1732, 1721 cm-1; 1H NMR δ 0.94 (t, 3H,
J ) 7.0 Hz), 1.08 (s, 3H), 1.10-1.65 (m, 6H), 1.75-2.15 (m,
5H), 2.32-2.44 (m, 1H), 5.64 (dd, 1H, J ) 6.0, 13.0 Hz), 7.43
(t, 2H, J ) 7.5 Hz), 7.55 (t, 1H, J ) 7.5 Hz), 8.09 (d, 2H, J )
7.5 Hz);
13C NMR δ 13.9, 19.4, 22.1, 23.3, 25.7, 33.3, 37.0, 40.1,
2-(Ben zoyloxy)-7,7-dim eth yl-1-oxospir o[4.4]n on an e (15).
10 (58 mg, 0.2 mmol) and BF3‚OEt2 (25 µL, 0.2 mmol) gave 15
49.6 (quaternary carbon), 74.9, 128.3, 129.8, 133.0, 165.7,
208.3. Anal. Calcd for C18H24O3: C, 74.97; H, 8.39. Found:
as a colorless oil (55.0 mg, 95%): IR 2953, 1752, 1723 cm-1
;
C, 74.93; H, 8.32. 25a : colorless oil; IR 2959, 2874, 1721 cm-1
;
1H NMR δ 1.09 (s, 3H), 1.10 (s, 3H), 1.42-1.98 (m, 7H), 2.01-
2.20 (m, 2H), 2.44-2.50 (m, 1H), 5.35 (t, 1H, J ) 9.0 Hz), 7.44
(t, 2H, J ) 7.5 Hz), 7.57 (t, 1H, J ) 7.5 Hz), 8.05 (d, 2H, J )
7.5 Hz); 13C NMR δ 26.4, 29.2, 29.5, 34.8, 37.5, 40.5, 41.5, 52.7,
54.7 (spiro carbon), 75.5, 128.4, 129.6, 129.9, 133.2, 165.9,
216.9. Anal. Calcd for C18H22O3: C, 75.50; H, 7.74. Found:
C, 75.19; H, 7.85.
1H NMR δ 0.90 (t, 3H, J ) 7.5 Hz), 1.30 (s, 3H), 1.25-1.35 (m,
2H), 1.50-1.87 (m, 6H), 2.15-2.20 (m, 2H), 2.55 (t, 2H, J )
7.5 Hz), 5.64 (t, 1H, J ) 6.0 Hz), 7.44 (t, 2H, J ) 7.5 Hz), 7.57
(t, 1H, J ) 7.5 Hz), 8.03 (d, 2H, J ) 7.5 Hz). Anal. Calcd for
C18H24O3: C, 74.97; H, 8.39. Found: C, 75.02; H, 8.41.
3-Bu tyl-3-m eth yl-2-oxocycloh ex-1-yl p-Nitr oben zoa te
(24b) a n d 2-Meth yl-2-(1-oxop en tyl)cyclop en t-1-yl p-Ni-
tr oben zoa te (25b). 21b (50 mg, 0.15 mmol) and BF3‚OEt2
(19 µL, 0.15 mmol) gave 24b (17 mg, 34%) and 25b (12 mg,
24%). 24b: colorless oil; IR 2938, 1736, 1721 cm-1; 1H NMR δ
0.95 (t, 3H, J ) 7.0 Hz), 1.08 (s, 3H), 1.10-1.65 (m, 6H,), 1.80-
2.15 (m, 5H), 2.35-2.50 (m, 1H), 5.65 (dd, 1H, J ) 6.5, 12.5
Hz), 8.25 (d, 2H, J ) 9.0 Hz), 8.28 (d, 2H, J ) 9.0 Hz). Anal.
Calcd for C18H23NO5: C, 64.84; H, 6.95; N, 4.22. Found: C,
2-(Ben zoyloxy)-1-oxosp ir o[4.5]d eca n e (16). 11 (47.2 mg,
0.173 mmol) and BF3‚OEt2 (20 µL, 0.173 mmol) gave 16 as a
white powder (46.7 mg, 99%): mp 62-63 °C (hexane/ethyl
acetate); IR 2930, 2857, 1752, 1721 cm-1 1H NMR δ 1.33-
;
2.60 (m, 14H), 5.43 (dd, 1H, J ) 8.0, 11.0 Hz), 7.39-7.57 (m,
3H), 8.04-8.09 (m, 2H); 13C NMR δ 22.6, 22.8, 26.4, 26.7, 30.1,
32.5, 35.5, 48.2 (spiro carbon), 77.0, 129.3, 130.5, 130.8, 134.1,