3
764 J . Org. Chem., Vol. 62, No. 11, 1997
Notes
+
7.41 (m, 5H); 13C NMR (CDCl
29.1, 39.1, 42.9, 44.9, 45.4, 76.4, 127.9, 128.2, 128.4, 131.6, 135.4,
(
7
M , 24), 268 (81), 195 (100). Anal. Calcd for C20
H
22
O
5
: C,
3
) δ -5.0, -4.7, 18.1, 24.1, 25.7,
0.16; H, 6.48. Found: C, 70.03; H, 6.48.
,3a ,4,5-Tet r a h yd r o-5-oxo-6-(2-p yr id yl)-2,2(1H )-p en t a l-
en ed ica r boxylic Acid Dieth yl Ester (2c). White solid; mp
-
1
3
182.5, 209.2; IR (KBr) 1712, 1670 cm ; MS, m/z (relative in-
+
tensity, %) 356 (M , 2), 300 (46), 299 (84), 73 (100). Anal. Calcd
1
7
(
1
2
1
2
6-78 °C (hexane/ether); R
CDCl ) δ 1.24 (t, J ) 7.0 Hz, 3H, CH
f
0.19 (hexane/ether ) 1/1); H NMR
for C22
H
32
O
2
Si: C, 74.11; H, 9.05. Found: C, 74.09; H, 9.03.
0.10
) δ -0.55 (s, 3H, SiMe ),
3
3
), 1.30 (t, J ) 7.0 Hz, 3H),
tr a n s-4b: White solid; mp 99-101 °C (hexane/ether); R
(hexane/ether ) 5/1); H NMR (CDCl
f
1
.74 (t, J ) 13 Hz, 1H), 2.32 (dd, J ) 3.5 Hz, J ) 18 Hz, 1H),
.85 (dd, J ) 6.8 Hz, J ) 18 Hz, 1H), 2.88 (dd, J ) 7.0 Hz, J )
3 Hz, 1H), 3.13-3.28 (m, 1H), 3.78 (s, 2H), 4.19 (q, J ) 7.0 Hz,
H), 4.26 (dq, J ) 1.9 Hz, J ) 7.0 Hz, 2H), 7.19 (dd, J ) 1.9 Hz,
3
2
-0.03 (s, 3H), 0.73 (s, 9H), 1.02 (s, 3H), 1.20 (s, 3H), 1.41 (dd, J
) 5.4 Hz, J ) 13 Hz, 1H), 2.07 (dd, J ) 2.7 Hz, J ) 13 Hz, 1H),
2.16 (dd, J ) 3.5 Hz, J ) 18 Hz, 1H), 2.81 (dd, J ) 7.0 Hz, J )
J ) 4.9 Hz, 1H), 7.70 (dt, J ) 1.9 Hz, J ) 7.8 Hz, 1H), 8.12 (d,
18 Hz, 1H), 2.94-3.05 (m, 1H), 4.66 (s,1H), 7.19-7.35 (m, 5H);
1
3
13
J ) 7.8 Hz, 1H), 8.64 (d, J ) 4.9 Hz, 1H); C NMR (CDCl
3
) δ
3
C NMR (CDCl ) δ -5.1, -5.0, 18.1, 25.0, 26.0, 28.5, 35.2, 43.0,
1
1
1
3
4.0, 14.1, 37.5, 38.7, 42.9, 43.4, 61.3, 61.9, 62.0, 122.5, 122.9,
43.8, 44.1, 80.5, 127.4, 127.8, 129.9, 131.4, 136.7, 181.2, 208.6;
IR (KBr) 1713, 1673, 1602 cm ; MS, m/z (relative intensity, %)
356 (M , 0.2), 300 (34), 299 (72), 73 (100). Anal. Calcd for
-
1
33.6, 136.2, 149.5, 150.9, 171.0, 171.6, 185.7, 206.7; IR (KBr)
730, 1699, 1649 cm-1; MS, m/z (relative intensity, %) 343 (M ,
+
+
0), 270 (100). Anal. Calcd for C19
H
21NO
5
: C, 66.46; H, 6.16;
C
22
H
32
O
2
Si: C, 74.11; H,9.05. Found: C, 74.04; H, 9.04.
N, 4.08. Found: C, 66.17; H, 6.16; N, 4.07.
,3a ,4,5-Tetr a h yd r o-5-oxo-6-(2-th ia zolyl)-2,2(1H)-p en ta l-
en ed ica r boxylic Acid Dieth yl Ester (2d ). White solid; mp
4-[[1,1-Dim eth yleth yl)dim eth ylsilyl]oxy]-4,5,6,6a-tetr ah y-
3
d r o-3,5,5-tr im eth yl-2(1H)-p en ta len on e (4c). GC analysis of
the grude reaction mixture showed that a mixture of cis-4c and
trans-4c was produced in a ratio of 2.4:1. Both isomers can be
separated easily by column chromatography on silica gel (hex-
1
7
9-81 °C (hexane/ether); R
f
0.10 (hexane/ether ) 2/1); H NMR
(
(
(
CDCl
3
) δ 1.25 (t, J ) 7.0 Hz, 3H), 1.30 (t, J ) 7.3 Hz, 3H), 1.82
t, J ) 12 Hz, 1H), 2.33 (dd, J ) 3.5 Hz, J ) 18 Hz, 1H), 2.87
dd, J ) 6.2 Hz, J ) 18 Hz, 1H), 2.90 (dd, J ) 7.3 Hz, J ) 12
ane/ether ) 7/1). cis-4c: Colorless oil; R
f
0.26 (hexane/ether )
) δ 0.01 (s, 3H), 0.10 (s, 3H), 0.80 (s, 3H,
), 0.88 (s, 9H), 1.03 (dd, J ) 7.0 Hz, J ) 13 Hz, 1H), 1.12 (s,
1
7/1); H NMR (CDCl
CH
3
Hz, 1H), 3.19-3.36 (m, 1H), 3.80 (t, J ) 22 Hz, 2H), 4.21 (dq, J
)
)
3
0.81 Hz, J ) 7.0 Hz, 2H), 4.27 (q, J ) 7.3 Hz, 2H), 7.41 (d, J
3H), 1.75 (d, J ) 2.4 Hz, 3H), 1.99 (dd, J ) 3.0 Hz, J ) 18 Hz,
1H), 2.00 (dd, J ) 2.4 Hz, J ) 13 Hz, 1H), 2.71 (dd, J ) 6.8 Hz,
1
3
3
3.2 Hz, 1H), 7.95 (d, J ) 3.2 Hz, 1H); C NMR (CDCl ) δ
J ) 18 Hz, 1H), 3.16-3.32 (m, 1H), 4.09 (s, 1H); 13C NMR (CDCl
)
1
1
1
3.9, 14.0, 37.1, 38.7, 41.7, 43.9, 61.4, 62.0, 62.1, 119.6, 129.0,
42.9, 157.1, 170.6, 171.4, 183.4, 205.0; IR (KBr) 1731, 1702,
3
δ -4.9, -4.7, 8.9, 18.1, 24.0, 25.7, 29.0, 39.3, 43.0, 44.0, 45.1,
-
1
+
-1
658 cm ; MS, m/z (relative intensity, %) 349 (M , 37), 276
S: C,58.44; H, 5.48; N, 4.01.
Found: C, 58.45; H, 5.39; N, 4.04.
,3a ,4,5-Tetr a h yd r o-5-oxo-6-m eth yl-2,2(1H)-p en ta len ed i-
ca r boxylic Acid Dieth yl Ester (2e). Colorless oil; R 0.11
) δ 1.25 (t, J ) 7.3 Hz,
76.2, 131.9, 180.8, 211.7; IR (neat) 1712, 1678 cm ; MS, m/z
+
(100). Anal. Calcd for C17
H
19NO
5
(relative intensity, %) 294 (M , 1), 237 (24), 75 (100). Anal. Calcd
for C17
tr a n s-4c: Colorless oil; R
(CDCl ) δ 0.12 (s, 6H), 0.83 (s, 3H), 0.95 (s, 9H), 1.15 (s, 3H),
30 2
H O Si: C, 69.33; H, 10.27. Found: C, 69.22; H, 10.26.
1
3
f
0.14 (hexane/ether ) 7/1); H NMR
f
3
1
(
3
3
hexane/ether ) 2/1); H NMR (CDCl
3
1.24 (dd, J ) 4.9 Hz, J ) 13 Hz, 1H), 1.82 (t, J ) 2.2 Hz), 1.94
(dd, J ) 3.2 Hz, J ) 13 Hz, 1H), 1.96 (dd, J ) 3.2 Hz, J ) 18
Hz, 1H), 2.63 (dd, J ) 6.8 Hz, J ) 18 Hz, 1H), 2.72-2.87 (m,
H), 1.27 (t, J ) 7.3 Hz, 3H), 1.63 (t, J ) 13 Hz, 1H), 1.70 (bs,
H), 2.07 (dd, J ) 3.3 Hz, J ) 18 Hz, 1H), 2.63 (dd, J ) 6.3 Hz,
1H), 4.57 (s, 1H); 13C NMR (CDCl
) δ -4.6, -4.5, 7.8, 18.0, 24.6,
J ) 18 Hz, 1H), 2.77 (dd, J ) 5.3 Hz, J ) 13 Hz, 1H), 2.89-3.03
3
(
(
m, 1H), 3.14 (d, J ) 19 Hz, 1H), 3.23 (d, J ) 19 Hz, 1H), 4.19
25.9, 28.8, 35.2, 43.4, 43.7, 43.8, 80.4, 132.2, 180.1, 210.9; IR
13
-1
+
q, J ) 7.3 Hz, 2H), 4.23 (q, J ) 7.3 Hz, 2H); C NMR (CDCl
3
)
(neat) 1711, 1673 cm ; MS, m/z (relative intensity, %) 279 (M
δ 8.4, 13.9, 33.9, 39.1, 41.3, 42.6, 60.9, 61.8, 61.9, 132.8, 170.9,
1
30 2
- 15, 1), 73 (100). Anal. Calcd for C17H O Si: C, 69.33; H,
10.27. Found: C, 69.19; H, 10.32.
3a ,4-Dih yd r o-6-(tr im eth ylsilyl)-1H-cyclop en ta [c]fu r a n -
-1
71.5, 177.7, 209.3; IR (neat) 1723, 1672 cm ; MS, m/z (relative
+
intensity, %) 280 (M , 12), 206 (43), 133 (100); exact mass calcd
for C15 280.1311, found 280.1311.
,3a ,4,5-Tetr a h yd r o-5-oxo-2,2(1H)-p en ta len ed ica r boxy-
lic Acid Dieth yl Ester (2g). Colorless oil; R 0.17 (hexane/
) δ 1.24 (t, J ) 7.0 Hz, 3H), 1.27 (t,
1
H
20
O
5
5(3H)-on e (6a ). Colorless oil; R
f
0.17 (hexane/ether ) 2/1); H
3
NMR (CDCl
3
) δ 0.18 (s, 9H), 2.09 (dd, J ) 3.8 Hz, J ) 18 Hz,
1H), 2.60 (dd, J ) 5.1 Hz, J ) 18 Hz, 1H), 3.20-3.25 (m, 2H,
3-H), 4.30 (t, J ) 14 Hz, 1H), 4.47 (d, J ) 16 Hz, 1H, 1-H), 4.65
f
1
ether ) 1/1); H NMR (CDCl
3
(d, J ) 16 Hz, 1H, 1-H); 13C NMR (CDCl
) δ -1.6, 40.2, 47.0,
1
J ) 7.0 Hz, 3H), 1.72 (t, J ) 13 Hz, 1H), 2.11 (dd, J ) 3.5 Hz,
J ) 18 Hz, 1H), 2.62 (dd, J ) 6.2 Hz, J ) 18 Hz, 1H), 2.78 (dd,
J ) 7.8 Hz, J ) 13 Hz, 1H), 3.02-3.17 (m, 1H), 3.23 (d, J ) 19
Hz, 1H), 3.34 (d, J ) 19 Hz, 1H), 4.19 (q, J ) 7.0 Hz, 2H), 4.23
3
-
66.1, 71.4, 136.1, 191.2, 212.7; IR (neat) 1705, 1622 cm ; MS,
+
m/z (relative intensity, %) 196 (M , 4), 181 (30), 75 (100); exact
mass calcd for C10
16 2
H O Si 196.0920, found 196.0913.
1
3
(
q, J ) 7.0 Hz, 2H), 5.92 (d, J ) 1.4 Hz, 1H); C NMR (CDCl
3
)
3a ,4-Dih yd r o-6-p h e n yl-1H -cyclop e n t a [c]fu r a n -5(3H )-
1
δ 13.9, 35.1, 38.8, 42.1, 45.0, 60.7, 61.9, 62.1, 125.5, 170.7, 171.4,
85.5, 209.5; IR (neat) 1733, 1638 cm ; MS, m/z (relative
intensity, %) 266 (M , 15), 119 (100). Anal. Calcd for
: C, 63.15; H, 6.81. Found: C, 63.21; H, 6.96.
cis-5,5-Dim et h yl-4-[[(1,1-d im et h ylet h yl)d im et h ylsilyl]-
oxy]-4,5,6,6a -tetr a h yd r o-3-(tr im eth ylsilyl)-2(1H)-p en ta le-
on e (6b). Colorless oil; R
f
0.21 (hexane/ether ) 1/1); H NMR
) δ 2.34 (dd, J ) 3.5 Hz, J ) 18 Hz, 1H), 2.85 (dd, J ) 6.2
-
1
1
(CDCl
3
+
Hz, J ) 18 Hz, 1H), 3.20-3.39 (m, 2H), 4.38 (t, J ) 7.0 Hz, 1H),
4.59 (d, J ) 16 Hz, 1H), 4.94 (d, J ) 16 Hz, 1H), 7.35-7.55 (m,
14 18 5
C H O
5H); 13C NMR (CDCl
) δ 40.1, 43.1, 66.1, 71.2, 127.9, 128.4,
3
1
-
130.5, 134.4, 177.3, 206.7; IR (neat) 1709, 1656, 1601 cm ; MS,
1
+
n on e (4a ). Colorless oil; R
(
0
1
2
f
0.31 (hexane/ether ) 10/1); H NMR
m/z (relative intensity, %) 200 (M , 34), 142 (100), 115 (88); exact
CDCl ) δ 0.02 (s, 3H), 0.11 (s, 3H), 0.22 (s, 9H), 0.76 (s, 3H),
3
12 2
mass calcd for C13H O 200.0837, found 200.0846.
2,3,3a ,4-Tetr a h yd r o-2-[(4-m eth ylp h en yl)su lfon yl]-6-(tr i-
.88 (s, 3H), 1.05 (dd, J ) 5.9 Hz, J ) 12 Hz, 1H), 1.13 (s, 3H),
.98 (dd, J ) 4.0 Hz, J ) 18 Hz, 1H), 2.02 (t, J ) 12 Hz, 1H),
m eth ylsilyl)cyclopen ta[c]pyr r ol-5(1H)-on e (8a). White solid;
1
.67 (dd, J ) 6.9 Hz, J ) 18 Hz, 1H), 3.33-3.43 (m, 1H), 4.16
mp 95-96 °C (hexane/ether); R
f
0.30 (hexane/ether ) 1/2); H
1
3
(s, 1H); C NMR (CDCl
3
) δ -4.7, -4.1, -0.9, 18.2, 24.1, 25.7,
NMR (CDCl
3
) δ 0.11 (s, 9H), 1.97 (dd, J ) 3.9 Hz, J ) 17 Hz,
2
1
(
8.5, 42.1, 42.2, 44.1, 46.1, 77.4, 135.9, 195.0, 215.7; IR (neat)
1H), 2.39 (s, 3H), 2.49 (dd, J ) 6.8 Hz, J ) 17 Hz, 1H), 2.56 (dd,
J ) 1.4 Hz, J ) 11 Hz, 1H), 2.92-3.08 (m, 1H), 3.95 (t, J ) 11
Hz, 1H), 3.98 (d, J ) 17 Hz, 1H), 4.26 (d, J ) 17 Hz, 1H), 7.32
-
1
+
699, 1621 cm ; MS, m/z (relative intensity, %) 352 (M , 3), 73
Si C, 64.71; H, 10.29.
100). Anal. Calcd for
C
19
H
36
O
2
2
:
Found: C 64.78; H 10.13.
(d, J ) 8.4 Hz, 2H), 7.69 (d, J ) 8.4 Hz, 2H); 13C NMR (CDCl
3
)
5
,5-Dim et h yl-4-[[1,1-d im et h ylet h yl)d im et h ylsilyl]oxy]-
δ -1.7, 21.4, 40.5, 45.2, 48.1, 52.0, 127.2, 129.8, 133.4, 137.8,
1
-
3
-p h en yl-4,5,6,6a -tetr a h yd r o-2(1H)-p en ta len on e (4b). GC
143.9, 185.3, 211.2; IR (KBr) 1696, 1632, 1601 cm ; MS, m/z
+
analysis of the crude reaction mixture showed that a mixture
of cis-4b and trans-4b was produced in a ratio of 26:1. Both
isomers can be separated easily by column chromatography on
(relative intensity, %) 349 (M , 6), 334 (34), 73 (100). Anal. Calcd
for C17
3
H23NO SSi: C, 58.42; H, 6.63; N, 4.01. Found: C, 58.12;
H, 6.69; N, 4.03.
silica gel (hexane/ether ) 5/1). cis-4b: White solid; mp 79-80
2,3,3a ,4-Tetr a h yd r o-2-[(4-m eth ylp h en yl)su lfon yl]-6-(d i-
m et h ylet h en ylsilyl)cyclop en t a [c]p yr r ol-5(1H )-on e (8b ).
1
°
C (hexane/ether); R
f
0.29 (hexane/ether ) 5/1); H NMR (CDCl
3
)
δ -0.18, -0.07 (s, 3H), 0.83 (s, 9H), 0.93 (s, 3H), 1.17 (s, 3H),
White solid; mp 53-55 °C (hexane/ether); R
f
0.16 (hexane/ether
) δ 0.21 (s, 3H), 0.23 (s, 3H), 1.99 (dd, J
1
1
1
7
.21 (dd, J ) 6.8 Hz, J ) 13 Hz, 1H), 2.13 (dd, J ) 1.4 Hz, J )
3 Hz, 1H), 2.20 (dd, J ) 3.2 Hz, J ) 18 Hz, 1H), 2.90 (dd, J )
.0 Hz, J ) 18 Hz, 1H), 3.37-3.47 (m, 1H), 4.35 (s, 1H), 7.29-
) 1/1); H NMR (CDCl
3
) 4.1 Hz, J ) 18 Hz, 1H), 2.43 (s, 3H), 2.53 (dd, J ) 6.5 Hz, J
) 18 Hz, 1H), 2.56 (dd, J ) 1.6 Hz, J ) 9.7 Hz, 1H), 2.96-3.12