3382 J . Org. Chem., Vol. 67, No. 10, 2002
Toyota et al.
(()-5-Ben zyloxym eth yl-7-m eth yl-cis-bicyclo[3.2.1]octa -
13C NMR δ: 197.25, 160.03, 144.44, 139.10, 123.00, 99.17,
96.55, 64.41, 57.51, 53.35, 52.27, 50.07, 35.57, 11.68. HRMS
calcd for C14H20O4 (M+): 252.1362. Found: 252.1324.
3,6-d ien -2-on e (30: X ) H, R ) -CH2OBn ). IR (neat) cm-1
:
1683. 1H NMR δ: 7.41-7.24 (5H, m), 7.29 (1H, dd, J ) 9.8,
1.6 Hz), 6.05 (1H, q, J ) 1.6 Hz), 5.40 (1H, dd, J ) 9.8, 1.6
Hz), 4.60 (2H, s), 3.55 (2H, dd, J ) 12.4, 9.1 Hz), 3.17 (1H, dd,
J ) 4.0, 1.2 Hz), 2.58-2.45 (2H, m), 1.79 (3H, d, J ) 1.6 Hz).
13C NMR δ: 157.50, 143.57, 138.20, 136.98, 137.02, 128.56,
127.86, 127.69, 122.30, 73.51, 72.72, 61.79, 53.57, 53.35, 15.47.
HRMS calcd for C17H18O2 (M+): 254.1307. Found: 254.1295.
(()-2-Met h oxy-4-(2-m et h oxym et h oxyet h yl)-4-(2-p r o-
pen yl)cycloh exa-2,5-dien -1-on e (31,X)OMe,R )-CH2CH2-
1
OMOM). IR (neat) cm-1: 1666. H NMR δ: 6.80 (1H, dd, J )
9.9, 2.5 Hz), 6.35 (1H, d, J ) 9.9 Hz), 5.67 (1H, d, J ) 2.5 Hz),
5.65-5.53 (1H, m), 5.09-5.01 (2H, m), 4.50 (2H, s), 3.67 (3H,
s), 3.37 (2H, td, J ) 6.9, 2.2 Hz), 3.29 (3H, s), 2.40 (2H, d, J )
7.4 Hz), 2.02 (2H, td, J ) 6.9, 2.2 Hz). 13C NMR δ: 181.53,
154.37, 151.97, 132.22, 129.15, 120.36, 119.18, 96.55, 64.08,
55.23, 54.79, 45.00, 44.75, 39.24. HRMS calcd for C14H20O4
(M+): 252.1362. Found: 252.1318.
(()-4-Ben zyloxym et h yl-4-(2-p r op en yl)cycloh exa -2,5-
d ien -1-on e (31: X ) H, R ) -CH2OBn ). IR (neat) cm-1
:
1664. 1H NMR δ: 7.40-7.22 (5H, m), 6.87 (1H, d, J ) 10.2
Hz), 6.87 (1H, dd, J ) 11.3, 4.7 Hz), 6.35 (1H, d, J ) 10.2 Hz),
6.35 (1H, dd, J ) 11.3, 4.7 Hz), 5.65-5.40 (1H, m), 5.10-5.00
(()-1-Met h oxy-7-m et h ylid en e-5-(2-m et h oxym et h oxy-
eth yl)-cis-bicyclo[3.2.1]oct-3-en -2-on e (29: X ) OMe, R )
-CH2CH2OMOM). IR (neat) cm-1: 1694. 1H NMR δ: 7.13
(1H, dd, J ) 9.6, 2.1 Hz), 5.93 (1H, d, J ) 9.6 Hz), 5.38 (1H,
dd, J ) 3.0, 1.9 Hz), 5.22 (1H, br s), 4.62 (2H, s), 3.69 (2H, t,
J ) 6.3 Hz), 3.39 (3H, s), 3.36 (3H, s), 2.46 (1H, ddd, J ) 17.0,
2.6, 2.6 Hz), 2.42 (1H, ddd, J ) 15.8, 4.0, 1.8 Hz), 2.24 (1H,
dd, J ) 10.6, 2.1 Hz), 2.09-1.88 (3H, m). 13C NMR δ: 196.42,
157.90, 144.10, 127.02, 113.07, 96.55, 90.74, 64.64, 55.37,
52.36, 46.35, 43.72, 41.78, 37.71. MS m/z: 252 (M+). Found:
252.1346. Anal. Calcd for C14H20O4: C, 66.65; H, 7.99. Found:
C, 66.32; H, 7.79.
(2H, m), 4.52 (2H, s), 3.45 (2H, s), 2.46 (2H, d, J ) 7.4 Hz). 13
C
NMR δ: 168.59, 151.88, 137.74, 132.06, 130.65, 128.57, 127.95,
127.63, 119.12, 74.51, 73.57, 39.68, 33.85. HRMS calcd for
C
17H18O2 (M+): 254.1307. Found: 254.1295.
(()-3-[7-Meth yl-2-oxo-cis-bicyclo[3.2.1]octa -3,6-d ien -5-
yl]p r op yl 2,2-Dim et h ylp r op a n oa t e (30: X ) H, R
)
-CH2CH2CH2OP v). IR (neat) cm-1: 1729, 1683. H NMR δ:
7.13 (1H, dd, J ) 9.6, 1.6 Hz), 5.94 (1H, d, J ) 1.6 Hz), 5.38
(1H, dd, J ) 9.6, 1.9 Hz), 4.13-4.09 (2H, m), 3.16 (1H, dd, J
) 4.0, 1.6 Hz), 2.50 (1H, d, J ) 9.6 Hz), 2.45 (1H, dd, J ) 4.4,
1.6 Hz), 1.78 (3H, d, J ) 1.64 Hz), 1.75-1.61 (3H, m), 1.21
(9H, s). 13C NMR δ: 200.05, 178.67, 159.71, 143.12, 138.97,
122.23, 64.20, 62.00, 54.76, 51.90, 38.66, 31.61, 27.08, 24.61,
15.42. MS m/z: 276 (M+). Anal. Calcd for C17H24O3: C, 73.88;
H, 8.75. Found: C, 73.67; H, 8.82.
1
(()-7-Meth yl-5-[2-(tr im eth ylsilyl)eth oxym eth oxy]-cis-
bicyclo[3.2.1]octa -3,6-d ien -2-on e (30: X ) H, R ) OSEM).
1
IR (neat) cm-1: 1683. H NMR δ: 7.36 (1H, dd, J ) 10.2, 2.2
Hz), 6.21-6.18 (1H, m), 5.31 (1H, dd, J ) 10.2, 2.2 Hz), 4.86
(2H, dd, J ) 10.7, 7.4 Hz), 3.76-3.62 (2H, m), 3.25 (1H, dd, J
) 4.4, 2.2 Hz), 2.83 (1H, dd, J ) 4.4, 2.2 Hz), 2.76 (1H, d, J )
9.3 Hz), 1.80 (3H, d, J ) 1.9 Hz), 0.98-0.92 (2H, m), 0.03 (9H,
s). 13C NMR δ: 199.06, 158.50, 142.83, 137.12, 120.59, 90.91,
87.20, 65.51, 61.26, 56.55, 18.05, 15.74, -1.57. HRMS calcd
for C12H15O3 (M+ - 73): 207.1021. Found: 207.0838.
(()-3-[1-Oxo-4-(2-p r op en yl)cycloh exa -2,5-d ien -4-yl]pr o-
p yl 2,2-Dim et h ylp r op a n oa t e (31: X ) H, R ) -CH 2-
1
CH2CH2OP v). IR (neat) cm-1: 1728, 1667. H NMR δ: 6.72
(1H, d, J ) 10.3 Hz), 6.72 (1H, dd, J ) 11.2, 4.9 Hz), 6.36 (1H,
d, J ) 10.3 Hz), 6.36 (1H, dd, J ) 11.2, J ) 4.9 Hz), 5.65-5.51
(1H, m), 5.08-5.01 (2H, m), 3.99 (2H, t, J ) 6.5 Hz), 2.37 (2H,
d, J ) 7.4 Hz), 1.74-1.68 (2H, m), 1.54-1.41 (2H, m), 1.19
(9H, s). 13C NMR δ: 186.49, 178.63, 153.85, 132.05, 130.67,
119.13, 63.84, 45.41, 44.02, 38.68, 34.96, 27.10, 23.95. HRMS
calcd for C17H24O3 (M+): 276.1725. Found: 276.1766.
(()-4-(2-P r open yl)-4-[2-(tr im eth ylsilyl)eth oxym eth oxy]-
cycloh exa -2,5-d ien -1-on e (31: X ) H, R ) OSEM). IR (neat)
1
cm-1: 1670. H NMR δ: 6.82 (1H, d, J ) 10.2 Hz), 6.82 (1H,
dd, J ) 11.4, 3.1 Hz), 6.28 (1H, d, J ) 10.2 Hz), 6.28 (1H, dd,
J ) 11.4, 5.0 Hz), 5.78-5.64 (1H, m), 5.16-5.05 (2H, m), 4.61
(2H, s), 3.68-3.62 (2H, m), 2.50 (2H, dt, J ) 7.1, 1.1 Hz), 0.95-
0.89 (2H, m), 0.03 (9H, s). 13C NMR δ: 185.72, 150.53, 130.99,
129.97, 119.80, 91.59, 74.83, 65.72, 43.96, 17.97, -1.61. HRMS
calcd for C15H24O3Si (M+): 280.1495. Found: 280.1483.
4-ter t-Bu tyld im eth ylsiloxya llylben zen e (33: X ) H). 1H
NMR δ: 7.03 (2H, d, J ) 9.0 Hz), 6.98 (2H, d, J ) 9.0 Hz),
6.02-5.90 (1H, m), 5.10-5.00 (2H, m), 3.33 (2H, d, J ) 7.0
Hz), 0.98 (9H, s), 0.18 (6H, s).
(()-7-Me t h y lid e n e -5-m e t h o x y m e t h o x y m e t h y l-ci s-
bicyclo[3.2.1]oct-3-en -2-on e (29: X ) H, R ) -CH2OMOM)
1
IR (neat) cm-1: 1683. H NMR δ: 7.15 (1H, dd, J ) 9.6, 1.9
Hz), 5.86 (1H, dd, J ) 9.6, 1.9 Hz), 5.30 (1H, br s), 5.07 (1H,
br s), 4.68 (2H, s), 3.66 (2H, dd, J ) 15.2, 9.4 Hz), 3.49 (1H, d,
J ) 4.9 Hz), 3.40 (3H, s), 2.48-2.41 (2H, m), 2.16 (1H, dd, J )
11.3, 2.2 Hz), 1.85 (1H, ddd, J ) 11.3, 4.9, 1.9 Hz). MS m/z:
208 (M+). Anal. Calcd for C12H13O3: C, 69.21; H, 7.74. Found:
C, 69.15; H, 7.92.
(()-7-Meth yliden e-5-[2-(tr im eth ylsilyl)eth oxym eth oxy]-
cis-bicyclo[3.2.1]oct-3-en -2-on e (29: X ) H, R ) OSEM).
(()-7-Met h yl-5-m et h oxym et h oxym et h yl-cis-b icyclo-
[3.2.1]oct-3,6-d ien -2-on e (30: X ) H, R ) -CH2OMOM).
1
IR (neat) cm-1: 1694. H NMR δ: 7.27 (1H, dd, J ) 10.2, 2.5
Hz), 5.82 (1H, dd, J ) 10.2, 1.8 Hz), 5.27 (1H, br s), 5.10 (1H,
br s), 4.86 (2H, dd, J ) 9.5, 7.6 Hz), 3.77-3.62 (2H, m), 3.51
(1H, d, J ) 5.2 Hz), 2.78 (1H, ddd, J ) 15.6, 2.7, 2.7 Hz), 2.64
(1H, ddd, J ) 15.6, 4.5, 2.5 Hz), 2.43 (1H, dd, J ) 10.7, 2.5
Hz), 2.15 (1H, ddd, J ) 10.7, 5.5, 2.5 Hz), 0.95 (2H, t, J ) 8.5
Hz), 0.03 (9H, s). 13C NMR δ: 197.68, 157.34, 142.01, 126.34,
113.38, 91.64, 82.88, 65.61, 58.02, 44.57, 41.38, 18.00, -1.58.
1
IR (neat) cm-1: 1683. H NMR δ: 7.28 (1H, dd, J ) 9.9, 1.6
Hz), 6.04 (1H, q, J ) 1.9 Hz), 5.42 (1H, dd, J ) 9.9, 1.6 Hz),
4.67 (2H, s), 3.65 (2H, dd, J ) 13.1, 9.4 Hz), 3.40 (3H, s), 3.19
(1H, dd, J ) 4.1, 1.5 Hz), 2.58-2.48 (2H, m), 1.80 (3H, d, J )
1.9 Hz). 13C NMR δ: 199.90, 157.09, 143.77, 136.79, 136.73,
122.38, 96.75, 70.30, 61.77, 55.26, 53.01, 15.44. HRMS calcd
for C12H16O3 (M+): 208.1099. Found: 208.1107.
-
MS (EI) m/z: 207 (M+ 73). Anal. Calcd for C15H24O3Si: C,
(()-4-Meth oxym eth oxym eth yl-4-(2-pr open yl)cycloh exa-
2,5-d ien -1-on e (31: X ) H, R ) -CH2OMOM). IR (neat)
64.24; H, 8.63. Found: C, 64.24; H, 8.61.
(()-2-Meth yl-4-m eth oxym eth oxym eth yl-4-(2-pr open yl)-
1
cm-1: 1666. H NMR δ: 6.86 (1H, d, J ) 10.4 Hz), 6.85 (1H,
cycloh exa -2,5-d ien -1-on e (31: X ) Me, R ) -CH2OMOM).
dd, J ) 11.2, 4.8 Hz), 6.36 (1H, d, J ) 10.4 Hz), 6.37 (1H, dd,
J ) 11.2, 4.8 Hz), 5.66-5.52 (1H, m), 5.10-5.04 (2H, m), 4.60
(2H, s), 3.55 (2H, s), 3.34 (3H, s), 2.65 (2H, dt, J ) 7.4, 1.0
Hz). 13C NMR δ: 186.36, 151.62, 131.85, 130.80, 119.25, 96.69,
72.16, 55.49, 46.14, 39.74. HRMS calcd for C12H16O3 (M+):
208.1099. Found: 208.1066.
1
IR (neat) cm-1: 1667. H NMR δ: 6.84 (1H, dd, J ) 9.9, 3.0
Hz), 6.64-6.62 (1H, m), 6.35 (1H, d, J ) 9.9 Hz), 5.64-5.44
(1H, m), 5.10-5.02 (2H, m), 4.59 (2H, s), 3.51 (2H, d, J ) 1.1
Hz), 3.34 (3H, s), 2.42 (2H, d, J ) 7.1 Hz), 1.92 (3H, d, J ) 1.4
Hz). 13C NMR δ: 151.39, 146.90, 132.29, 130.43, 118.90, 96.68,
72.42, 55.37, 45.95, 39.87. HRMS calcd for C13H18O3 (M+):
222.1256. Found: 222.1249.
(()-1-Met h oxy-7-m et h yl-5-(2-m et h oxym et h oxyet h yl)-
cis-bicyclo[3.2.1]octa -3,6-d ien -2-on e (30: X ) OMe, R )
-CH2CH2OMOM). IR (neat) cm-1: 1689. 1H NMR δ: 7.24
(1H, dd, J ) 9.6, 1.6 Hz), 6.07 (1H, dd, J ) 1.6, 0.8 Hz), 5.51
(1H, d, J ) 9.6 Hz), 4.63 (2H, s), 3.69 (2H, t, J ) 6.5 Hz), 3.37
(3H, s), 3.36 (3H, s), 2.71 (1H, d, J ) 9.1 Hz), 2.52 (1H, dd, J
) 9.1, 1.6 Hz), 2.12-1.90 (2H, m), 1.69 (3H, d, J ) 1.6 Hz).
(()-1-Meth yl-7-m eth yliden e-5-m eth oxym eth oxym eth yl-
cis-b icyclo[3.2.1]oct -3-en -2-on e (29:
X
)
Me,
R
)
-CH2OMOM). IR (neat) cm-1: 1683. 1H NMR δ: 7.12 (1H,
dd, J ) 9.6, 1.9 Hz), 5.89 (1H, d, J ) 9.9 Hz), 5.11-5.09 (2H,
m), 4.68 (2H, s), 3.64 (2H, dd, J ) 14.3, 9.3 Hz), 3.40 (3H, s),
2.61 (2H, dt, J ) 15.6, 2.5 Hz), 2.45 (1H, dq, J ) 15.6, 1.9 Hz),