Notes
J . Org. Chem., Vol. 67, No. 1, 2002 293
5
1
.24-5.22 (m, 1H), 3.44 (dd, J ) 9.6, 4.4 Hz, 1H), 2.73-2.66 (m,
H), 2.34 (s, 3H), 2.03 (ddd, J ) 13.2, 4.4, 1.2 Hz, 1H); 13C NMR
4,7-Dibr om o-3-oxo-2-oxa bicyclo[2.2.2]oct-7-en e-5-exo-6-
en d o-d ica r boxylic a cid d im eth yl ester (8b a n d 9b): H NMR
1
(100 MHz, CDCl
3
) δ 203.0, 165.4, 133.6, 117.8, 80.0, 57.6, 50.1,
(400 MHz, CDCl
3
) δ 6.81 (J ) 2.0 Hz, 1H), 5.48 (dd, J ) 4.0, 2.4
-
1
3
1
2.9, 31.8; FT-IR (KBr, cm ) 1766, 1725; HRMS (CI) m/z (M +
Hz, 1H), 3.81 (s, 6H), 3.72 (dd, J ) 5.6, 4.0 Hz, 1H), 3.64 (d, J )
+
13
)
calcd for C
9
H
9
Br
2
O
3
322.8918, found 322.8884.
5.6 Hz, 1H); C NMR (100 MHz, CDCl
3
) δ 170.0, 167.7, 163.9,
-1
8
-exo-Acet yl-4,6-d ibr om o-2-oxa bicyclo[2.2.2]oct -5-en -3-
136.7, 120.0, 79.5, 57.4, 53.7, 53.6, 51.5, 50.0; FT-IR (KBr, cm
)
-
1
+
on e (3b): H NMR (400 MHz, CDCl
5
3
3
) δ 6.73 (d, J ) 2.4 Hz, 1H),
.19-5.17 (m, 1H), 3.44 (dd, J ) 9.6, 6.0 Hz, 1H), 2.34 (s,
H), 2.31-2.30 (m, 1H), 2.28-2.27 (m, 1H); 13C NMR (100
) δ 205.8, 164.5, 135.7, 121.3, 79.3, 57.7, 53.0, 32.4,
1800, 1747, 1734; HRMS (CI) m/z (M + 1) calcd for C11
Br 396.8921, found 396.8902.
4,6-Dibr om o-8-en d o-eth oxy-2-oxa bicyclo[2.2.2]oct-5-en -
H
11
2 6
O
1
MHz, CDCl
2.3
,7-Dibr om o-3-oxo-2-oxa bicyclo[2.2.2]oct-7-en e-5-en d o-
3
3
3-on e (10a ): H NMR (400 MHz, CDCl ) δ 6.56 (d, J ) 2.4 Hz,
3
1H), 5.15-5.13 (m, 1H), 3.88 (ddd, J ) 7.6, 2.0, 1.2 Hz, 1H),
3.76-3.64 (m, 2H), 2.68 (ddd, J ) 13.6, 7.6, 3.6 Hz, 1H), 2.00
4
1
(ddd, J ) 13.6, 2.0, 2.0 Hz, 1H), 1.23 (t, J ) 7.0 Hz, 3H); 13
C
ca r bon itr ile (4a ): H NMR (400 MHz, CDCl
2
2
NMR (100 MHz, CDCl
3
1
3
) δ 6.83 (d, J )
.4 Hz, 1H), 5.28-5.26 (m, 1H), 3.46 (dd, J ) 9.6, 3.2 Hz, 1H),
3
NMR (100 MHz, CDCl ) δ 166.3, 133.6, 118.7, 79.8, 76.7, 67.7,
.87-2.80 (m, 1H), 2.40 (ddd, J ) 13.6, 3.2, 1.2 Hz, 1H); 13
64.4, 37.1, 15.7; FT-IR (KBr, cm-1) 1764; HRMS (CI) m/z (M +
C
+
) δ 163.6, 133.6, 121.5, 117.0, 78.9, 56.3,
1) calcd for C11
H
11Br
2
O
6
396.8921, found 396.8906.
3
-
1
4,6-Dibr om o-8-exo-eth oxy-2-oxa bicyclo[2.2.2]oct-5-en -3-
on e (10b): H NMR (400 MHz, CDCl ) δ 6.62 (d, J ) 2.4 Hz,
H), 5.11-5.09 (m, 1H), 3.91(dd, J ) 8.8, 2.4 Hz, 1H), 3.66(q, J
) 7.2, 2H), 2.39 (ddd, J ) 13.6, 8.8, 1.6 Hz, 1H), 2.22 (ddd, J )
4.8, 33.4; FT-IR (KBr, cm ) 2247, 1785; HRMS (CI) m/z (M +
+
1
)
calcd for C
8
H
6
Br
2
NO
2
305.8765, found 305.8736.
3
1
4
,7-Dib r om o-3-oxo-2-oxa b icyclo[2.2.2]oct -7-en e-5-exo-
1
ca r bon itr ile (4b): H NMR (400 MHz, CDCl
3
) δ 6.75 (d, J )
.4 Hz, 1H), 5.27 (ddd, J ) 4.8, 2.4, 1.6 Hz, 1H), 3.35 (dd, J )
1.2, 4.8 Hz, 1H), 2.74 (ddd, 13.6, 9.6, 4.8, 1H), 2.55 (ddd, J )
3.6, 11.2, 1.6 Hz, 1H); 13C NMR (100 MHz, CDCl
) δ 162.8,
34.1, 122.2, 116.5, 79.2, 59.5, 35.2, 33.2, 31.7, 22.8, 14.2
1
3.6, 4.0, 2.4 Hz, 1H), 1.21 (t, J ) 7.2 Hz, 3H); 13C NMR (100
2
1
1
1
MHz, CDCl
15.2.
3
) δ 164.6, 133.2, 121.9, 80.3, 77.8, 67.3, 63.6, 35.1,
3
en d o-8-Ben zyloxy-4,6-d ibr om o-2-oxa bicyclo[2.2.2]oct-5-
en -3-on e (11a ): 1H NMR (400 MHz, CDCl
5H), 6.60 (dd, J ) 2.4, 0.8 Hz, 1H), 5.11 (ddd, J ) 3.6, 2.4, 2.0
Hz, 1H), 4.75 (d, J ) 11.6 Hz, 1H), 4.70 (d, J ) 11.6 Hz, 1H),
.98 (ddd, J ) 8.0, 2.4, 0.8 Hz, 1H), 2.57 (ddd, J ) 14.0, 8.0, 3.6
) δ 7.39-7.31 (m,
,11-Dibr om o-4-eth yl-8-oxa-4-azatr icyclo[5.2.2.0 .6]u n dec-
2
3
1
1
1
3
0-en e-3,5,9-tr ion (5a ): H NMR (400 MHz, CDCl ); δ 6.72 (d,
J ) 2.0 Hz, 1H), 5.55 (dd, J ) 4.4, 2.4 Hz, 1H), 3.89 (dd, J )
8
Hz, 1H), 1.16 (t, J ) 7.2 Hz, 3H); C NMR (100 MHz, CDCl
1
FT-IR (KBr, cm ) 1769, 1742; HRMS (CI) m/z (M + 1) calcd
for C11 NO 377.8976, found 377.8944.
,11-Dibr om o-4-eth yl-8-oxa -4-a za tr icyclo[5.2.2.0]u n d ec-
3
.0, 4.4 Hz, 1H), 3.57 (qd, J ) 7.2, 1.2 Hz, 1H), 3.49 (d, J ) 8.0
13
1
3
Hz, 1H), 2.01 (ddd, J ) 14.0, 2.4, 2.0 Hz, 1H); C NMR (100
MHz, CDCl ) δ 165.6, 136.4, 133.1, 128.3, 128.0, 127.8, 118.4,
79.3, 75.5, 73.3, 63.8, 36.4; FT-IR (KBr, cm ) 1775; HRMS (CI)
3
) δ
70.4, 170.1, 163.9, 134.6, 118.2, 78.4, 55.5, 46.8, 45.1, 34.6, 12.7;
3
-
1
-
1
+
+
m/z (M + 1) calcd for C14
2 3
H13Br O 386.9231, found 386.9202.
H
10Br
2
4
4
.6-Dibr om o-8-en do-(4-br om op h en yl)-2-oxa bicyclo[2.2.2]-
1
1
1
oct-5-en -3-on e (12a ): H NMR (400 MHz, CDCl
8.4 Hz, 2H), 7.00 (d, J ) 8.4 Hz, 2H), 6.51 (d, J ) 2.4 Hz, 1H),
5.32-5.30 (m, 1H), 3.37 (dd, J ) 9.2, 4.4 Hz, 1H), 2.97-2.90 (m,
H), 2.23 (ddd, J ) 14.0, 4.4, 1.2 Hz, 1H); 13C NMR (100 MHz,
CDCl ) δ 166.4, 137.3, 133.6, 131.3, 130.4, 122.1, 120.2, 80.3,
3.4, 45.3, 36.7; FT-IR (KBr, cm ) 1781; HRMS (CI) m/z (M +
3
) δ 7.48 (d, J
1
0-en e-3,5,9-tr ion (5b): H NMR (400 MHz, CDCl
3
) δ 6.81 (d,
)
J ) 2.0 Hz, 1H), 5.54-5.52 (m, 1H), 3.57 (q, J ) 7.2 Hz, 2H),
.47 (bs, 1H), 3.47 (bs, 1H), 1.14 (t, J ) 7.2 Hz, 3H); 1 C NMR
100 MHz, CDCl ) δ 170.4, 169.6, 162.88, 136.6, 120.9, 79.5, 55.2,
7.8, 47.5, 34.6, 12.6
,7-Dibr om o-5-exo-m eth yl-3-oxo-2-oxa bicyclo[2.2.2]oct-
3
3
(
4
1
3
3
-
1
6
4
+
1
1) calcd for C13
3 2
H10Br O 434.8230, found 434.8199.
7
-en e-5-en d o-ca r boxylic a cid m eth yl ester (6a ): H NMR
) δ 6.75 (d, J ) 2.4 Hz, 1H), 5.18-5.16 (m, 1H),
.77 (s, 3H), 2.52 (dd, J ) 13.6, 1.2 Hz, 1H), 2.35 (dd, J ) 13.6,
4
.6-Dibr om o-8-exo-(4-br om op h en yl)-2-oxa bicyclo[2.2.2]-
(400 MHz, CDCl
3
1
oct-5-en -3-on e (12b): H NMR (400 MHz, CDCl
) 8.8 Hz, 2H), 7.04 (d, J ) 8.8 Hz, 2H), 6.86 (d, J ) 2.4 Hz, 1H),
.29-5.26 (m, 1H), 3.39 (dd, J ) 10.4, 5.6 Hz, 1H), 2.62 (ddd, J
) 14.0, 10.4, 1.6 Hz, 1H), 2.49 (ddd, J ) 14.0, 5.6, 4.0 Hz, 1H);
C NMR (100 MHz, CDCl ) δ 165.7, 136.7, 136.5, 131.7, 130.2,
3
22.3, 120.9, 80.4, 63.7, 48.2, 36.0.
3
) δ 7.47 (d, J
3
4
1
.0 Hz, 1H), 1.50 (s, 3H); 1 C NMR (100 MHz, CDCl
3
3
) δ 171.5,
5
65.1, 135.4, 117.9, 80.3, 65.7, 52.9, 48.6, 40.6, 23.8; FT-IR (KBr,
-
1
+
cm ) 1784, 1721; HRMS (CI) m/z (M + 1) calcd for C
3
9
H
11Br
2
O
4
1
3
52.9023, found 352.9015.
1
4
,7-Dibr om o-5-en d o-m eth yl-3-oxo-2-oxa bicyclo[2.2.2]oct-
1
4-Br om o-7-en do-(2-m eth oxycar bon ylvin yl)-3-oxabicyclo-
7
-en e-5-exo-ca r boxylic a cid m eth yl ester (6b): H NMR (400
) δ 6.66 (d, J ) 2.8 Hz, 1H), 5.15 (ddd, J ) 4.0, 2.8,
.2 Hz, 1H), 3.76 (s, 3H), 2.79 (dd, J ) 13.6, 4.0 Hz, 1H), 1.93
[
2.2.2]oct-7-en e-5-ca r boxylic Acid Meth yl Ester (15). A
mixture of 50 mg (0.147 mmol) of 1a , 0.015 mL (0.162 mmol) of
methyl acrylate, 3 mg (0.015 mmol) of Pd(OAc) , 9 mg (0.030
mmol) of tri(o-tolyl)phosphine, and 0.060 mL (0.441 mmol) of
Et N in 3 mL of anhydrous MeCN was refluxed for 1.5 h with
vigorous stirring. The reaction mixture was quenched with H
and extracted with CH Cl . The organic solution was dried over
MgSO and purified by column chromatography (hexane/ethyl
acetate: 1/1) to give 44 mg of the product 15 in 87% yield:
NMR (400 MHz, CDCl ) δ 7.29 (d, J ) 16.0 Hz, 1H), 6.78 (s,
MHz, CDCl
1
3
1
3
2
(
dd, J ) 13.6, 1.2 Hz, 1H), 1.45 (s, 3H); C NMR (100 MHz,
CDCl ) δ 172.2, 165.5, 135.1, 120.1, 78.9, 65.9, 53.2, 51.1, 39.3,
2
3
3
2.6
,7-Dibr om o-6-exo-m eth yl-3-oxo-2-oxa bicyclo[2.2.2]oct-
2
O
4
1
2
2
7
-en e-5-en d o-ca r boxylic a cid m eth yl ester (7a ): H NMR
) δ 6.67 (dd, J ) 2.4, 0.8 Hz, 1H), 4.87 (dd, J )
.4, 1.2 Hz, 1H), 3.79 (s, 3H), 2.72 (dd, J ) 4.8, 0.8 Hz, 1H),
.47-2.40 (m, 1H), 1.36 (d, J ) 6.8 Hz, 1H); C NMR (100 MHz,
) δ 170.2, 165.6, 133.7, 119.4, 85.3, 58.3, 54.1, 53.2, 41.9,
4
(400 MHz, CDCl
3
1
H
2
2
1
3
3
1
3
1
H), 6.13 (d, J ) 16.0 Hz, 1H), 5.58-5.57 (m, 1H), 3.79 (s, 3H),
.76 (s, 3H), 3.35 (ddd, J ) 10.0, 4.4, 0.8 Hz, 1H), 2.85-2.78 (m,
H), 1.97 (ddd, J ) 13.6, 4.8, 1.6 Hz, 1H); 13C NMR (100 MHz,
CDCl
8.2; FT-IR (KBr, cm-1) 1774, 1740; HRMS (CI) m/z (M + 1)
calcd for C 352.9023, found 352.9001.
,7-Dibr om o-6-en d o-m eth yl-3-oxo-2-oxa bicyclo[2.2.2]oct-
3
+
1
9
2 4
H11Br O
CDCl
3
) δ 170.1, 166.0, 165.9, 139.0, 137.4, 135.8, 120.1, 72.6,
4
-
1
5
7.8, 52.7, 51.9, 46.2, 33.3; FT-IR (KBr, cm ) 1764, 1749, 1724;
HRMS (EI) m/z (M ) calcd for C13
43.9895.
1
7
-en e-5-exo-ca r boxylic a cid m eth yl ester (7b): H NMR (400
+
4
H13BrO 343.9895, found
MHz, CDCl ) δ 6.84 (d, J ) 2.8 Hz, 1H), 5.36 (dd, J ) 4.0, 2.8
3
3
Hz, 1H), 3.79 (s, 3H), 3.10 (dd, J ) 4.8, 4.4 Hz, 1H), 2.73 (m,
1
1
H), 1.34 (d, J ) 4.4 Hz, 3H); 13C NMR (100 MHz, CDCl
68.6, 165.4, 137.5, 118.4, 80.2, 63.3, 52.8, 52.5, 40.8, 19.1
3
) δ
Ack n ow led gm en t. The financial support of the
Ministry of Science and Technology (National Research
Laboratory, 99-N-NL-01-C-103) in Korea is acknowl-
edged.
4
,7-Dibr om o-3-oxo-2-oxa bicyclo[2.2.2]oct-7-en e-5-en d o-
1
6
-exo-d ica r boxylic a cid d im eth yl ester (8a a n d 9a ): H NMR
) δ 6.72 (dd, J ) 2.4, 0.8 Hz, 1H), 5.52 (dd, J )
.4, 1.6 Hz, 1H), 3.84 (s, 3H), 3.81 (s, 3H), 3.81 (1H, overlapped
(400 MHz, CDCl
3
2
Su p p or tin g In for m a tion Ava ila ble: Spectral data of all
the new cycloadducts and 13. X-ray data of 9a and 9b. This
material is available free of charge via the Internet at
http://pubs.acs.org.
1
3
with CH
3
peak), 3.32 (dd, J ) 4.8, 1.6 Hz, 1H); C NMR (100
MHz, CDCl
3.5, 50.7, 48.23; FT-IR (KBr, cm ) 1786, 1758, 1737; HRMS
3
) δ 169.7, 167.9, 164.6, 135.2, 118.41, 81.6, 57.6, 54.0,
-
1
5
+
(
3
CI) m/z (M + 1) calcd for C11
2 6
H11Br O 396.8921, found
96.8925.
J O015804R