4
-Triflyloxy-2,6,6-trimethyl-2,4-cyclohexadienone
+
1
H), 2.70 (dd, J ) 9,6, 7.3 Hz, 1H), 2.61-2.57 (m, 1H), 2.28
91 (26), 77 (25); HRMS (EI) calcd for C11
found 209.1034.
(
3
H15NO (M ) 209.1052,
(
ddd, J ) 13.0, 9.6, 3.4 Hz, 1H), 2.05 (s, 3H), 1.46 (ddd, J )
1
3.0, 7.3, 2.5 Hz, 1H), 1.16 (s, 3H), 1.06 (s, 3H), 1.00 (s, 3H);
1S*,4S*,7S*)-1,3,3-Tr im eth yl-7-cya n obicyclo[2.2.2]oct-
-en -2-on e (1e). Following the procedure described for the
preparation of 1a , a mixture of 15e (135 mg, 0.40 mM), tri-
n-butylamine (229 mg, 1.24 mM), formic acid (51 mg, 1.10
3 2 2
mM), and Pd(PPh ) Cl (15 mg, 0.02 mM) in DMF (1 mL) was
used, and the residue was purified by column chromatography
on silica gel using 10% ethyl acetate in hexanes as an eluent
to obtain a yellowish oil 1e (58 mg, 77%): IR (neat) 2975, 2238,
1726, 1384, 1034 cm ; H NMR (400 MHz) δ 6.69 (dd, J )
8.0, 6.8 Hz, 1H), 5.85 (ddd, J ) 8.0, 1.4, 0.6 Hz, 1H), 2.71
(dd, J ) 10, 5.7 Hz, 1H), 2.70-2.60 (m, 1H), 2.51 (ddd, J )
14.3, 10.0, 3.1 Hz, 1H), 1.77 (ddd, J ) 14.3, 5.7, 2.7 Hz, 1H),
1.41 (s, 3H), 1.07 (s, 3H), 1.06 (s, 3H); 13C NMR (100 MHz) δ
213.0, 140.0, 129.5, 120.3, 50.1, 43.3, 42.8, 31.4, 29.0, 27.9, 24.1,
1
3
C NMR (100 MHz) δ 214.5, 208.1, 137.5, 129.4, 50.9, 50.6,
5
4
3.5, 43.1, 30.6, 28.4, 27.6, 24.7, 15.5; MS (EI) m/z (rel
+
intensity) 206 (M , 26), 136 (59), 135 (24), 121 (26), 93 (100),
9
2
+
2 (57), 43 (24), 18 (34); HRMS (EI) calcd for C13
06.1307, found 206.1308.
18 2
H O (M )
(
1S *,4S *,7S *)-1,3,3-Tr im e t h yl-7-m e t h oxyca r b on yl-
bicyclo[2.2.2]oct-5-en -2-on e (1b). Following the procedure
described for the preparation of 1a , a mixture of 15b (100 mg,
0
-
1
1
.27 mM), tri-n-butylamine (150 mg, 0.81 mM), formic acid
(
25 mg, 0.54 mM), and Pd(PPh Cl (10 mg, 0.014 mM) in
3
)
2
2
DMF (1 mL) was used, and the residue was purified by column
chromatography on silica gel using 5% ethyl acetate in hexanes
as an eluent to obtain a yellowish oil 1b (57 mg, 95%); IR (neat)
973, 1722, 1207, 1172 cm-1; H NMR (400 MHz) δ 6.57 (dd,
1
16.1; MS (EI) m/z (rel intensity) 189 (M , 10), 161 (60), 146
(74), 119 (72), 104 (51), 91 (78), 77 (57), 70(100), 41 (56), 39
+
2
J ) 8.0, 6.6 Hz, 1H), 5.71 (ddd, J ) 8.0, 1.3, 1.3 Hz, 1H), 3.64
+
(s, 3H), 2.64-2.59 (m, 2H), 2.32 (ddd, J ) 13.0, 9.7, 3.1 Hz,
(62); HRMS (EI) calcd for C12
189.1152.
H
15NO (M ) 189.1154, found
1
3
1
H), 1.66 (ddd, J ) 13.0, 7, 2.6 Hz, 1H), 1.20 (s, 3H), 1.08 (s,
H), 1.05 (s, 3H); 1 C NMR (100 MHz) δ 214.5, 174.1, 138.1,
3
(
1S*,4S*,7R*)-1,3,3-Tr im eth yl-7-cya n obicyclo[2.2.2]oct-
-en -2-on e (1e′). Following the procedure described for the
preparation of 1a , a mixture of 16e (112 mg, 0.33 mM), tri-
n-butylamine (183 mg, 0.99 mM), formic acid (46 mg, 0.98
3 2 2
mM), and Pd(PPh ) Cl (12 mg, 0.017 mM) in DMF (1 mL) was
used, and the residue was purified by column chromatography
on silica gel using 15% ethyl acetate in hexanes as an eluent
to obtain a yellowish oil 1e′ (58 mg, 93%): IR (neat) 2975, 2236,
1721, 1614, 1461, 1384 cm ; H NMR (400 MHz) δ 6.60 (dd,
J ) 8.0, 6.6 Hz, 1H), 5.78 (dd, J ) 8.0, 1.6 Hz, 1H), 2.67-2.63
(m, 1H), 2.60 (dd, J ) 12.0, 4.2 Hz, 1H), 2.35 (ddd, J ) 13.6,
4.2, 3.1 Hz, 1H), 1.98 (ddd, J ) 13.6, 12, 2.8 Hz, 1H), 1.38 (s,
3H), 1.22 (s, 3H), 1.10 (s, 3H); 13C NMR (100 MHz) δ 212.4,
140.3, 130.6, 120.1, 50.6, 43.9, 43.2, 32.1, 28.2, 27.7, 23.7, 16.4;
29.0, 51.7, 51.0, 43.6, 43.5, 43.1, 28.8, 27.8, 24.6, 15.6; MS
5
+
(EI) m/z (rel intensity) 222 (M , 12), 152 (74), 93 (100), 92 (30),
+
2
8 (44), 18 (99); HRMS (EI) calcd for C13
found 222.1257.
1S*,4S*,7S*)-1,3,3-Tr im eth yl-7-p h en ylsu lfon ylbicyclo-
2.2.2]oct-5-en -2-on e (1c). Following the procedure described
18 3
H O (M ) 222.1256,
(
[
for the preparation of 1a , a mixture of 15c (101 mg, 0.22 mM),
tri-n-butylamine (135 mg, 0.72 mM), formic acid (30 mg, 0.65
mM), and Pd(PPh ) Cl (10 mg, 0.014 mM) in DMF (1 mL) was
3 2 2
-
1 1
used, and the residue was purified by column chromatography
on silica gel using 25% ethyl acetate in hexanes as an eluent
to obtain a white solid 1c (64 mg, 98%): mp 169-170 °C; IR
neat) 2941, 1720, 1308, 1147 cm- ; H NMR (400 MHz) δ 7.83
J ) 5.8 Hz, 2H), 7.62-7.51 (m, 3H), 6.50 (dd, J ) 8.0, 6.8 Hz,
1 1
(
(
+
MS (EI) m/z (rel intensity) 189 (M , 78), 161 (41), 145 (65),
119 (96), 118 (25), 104 (22), 91 (23), 70 (28), 69 (100), 42 (29);
1
7
3
1
1
1
H), 5.77 (ddd, J ) 8.0, 1.2, 0.9 Hz, 1H), 3.35 (ddd, J ) 9.5,
.6, 0.9 Hz, 1H), 2.58-2.54 (m, 1H), 2.05 (ddd, J ) 13.8, 9.5,
.5 Hz, 1H), 1.78 (ddd, J ) 13.8, 7.6, 2.7 Hz, 1H), 1.50 (s, 3H),
.04 (s, 3H), 1.02 (s, 3H); 13C NMR (100 MHz) δ 212.4, 139.9,
37.4, 133.6, 129.2, 128.3, 62.2, 51.2, 42.8, 42.2, 28.3, 27.8, 24.6,
+
HRMS (EI) calcd for C12
H
15NO (M ) 189.1154, found 189.1154.
1S*,4S*,7S*)-1,3,3-Tr im et h yl-7-p h en ylb icyclo[2.2.2]-
oct-5-en -2-on e (1f). Following the procedure described for the
preparation of 1a , a mixture of 15f (125 mg, 0.33 mM), tri-n-
butylamine (180 mg, 0.97 mM), formic acid (45 mg, 0.98 mM),
(
+
6.5; MS (EI) m/z (rel intensity) 304 (M , 10), 163 (96), 146
(67), 134 (85), 93 (100), 92 (79), 91 (46), 76(47), 43 (50); HRMS
3 2 2
and Pd(PPh ) Cl (12 mg, 0.017 mM) in DMF (1 mL) was used,
+
(EI) calcd for C17
H
O
20
O
3
S (M ) 304.1133, found 304.1131. Anal.
and the residue was purified by column chromatography on
silica gel using 10% ethyl acetate in hexanes as an eluent to
obtain a yellowish oil 1f (63 mg, 82%): IR (neat) 2970, 1715,
1601, 1493, 1453, 1380, 1031 cm ; H NMR (400 MHz) δ 7.25-
7.14 (m, 5H), 6.70 (dd, J ) 8.0, 6.6 Hz, 1H), 5.74 (ddd, J )
8.0, 1.3, 1.3 Hz, 1H), 2.81 (dd, J ) 9.4, 7.3 Hz, 1H), 2.70-2.66
(m, 1H), 2.62 (ddd, J ) 13.3, 9.4, 3.4 Hz, 1H), 1.71 (ddd, J )
13.3, 7.3, 2.4 Hz, 1H), 1.22 (s, 3H), 1.11 (s, 3H), 0.85 (s, 3H);
Calcd for C17
6
H
20
3
S: C, 67.08; H, 6.62. Found: C, 67.12; H,
.63.
1S*,4S*,7S*)-1,3,3-Tr im eth yl-7-n itr obicyclo[2.2.2]oct-
-en -2-on e (1d ). Following the procedure described for the
-1 1
(
5
preparation of 1a , a mixture of 15d (74 mg, 0.21 mM), tri-n-
butylamine (174 mg, 0.64 mM), formic acid (30 mg, 0.65 mM),
and Pd(PPh ) Cl (10 mg, 0.014 mM) in DMF (1 mL) was used,
3 2 2
and the residue was purified by column chromatography on
silica gel using 10% ethyl acetate in hexanes as an eluent to
obtain a yellowish oil 1d (26 mg, 59%) along with compound
1
3
C NMR (100 MHz) δ 216.4, 143.4, 138.7, 129.8, 128.6, 128.1,
126.6, 53.6, 44.8, 44.1, 43.1, 34.0, 27.9, 25.1, 16.2; HRMS (EI)
+
calcd for C17
H20O (M ) 240.1514, found 240.1529.
1
1
1
1
2
3
9
d ′ (15 mg, 34%): IR (neat) 2976, 2929, 1726, 1553, 1384, 1367,
(
1S*,4S*,7R*)-1,3,3-Tr im eth yl-7-eth en ylbicyclo[2.2.2]-
-
1
1
034 cm ; H NMR (400 MHz) δ 6.62 (dd, J ) 8.0, 6.6 Hz,
H), 5.74 (dd, J ) 8.0, 1.6 Hz, 1H), 4.57 (dd, J ) 11.1, 4.8 Hz,
H), 2.70-2.65 (m, 1H), 2.39 (ddd, J ) 14.5, 4.8, 2.2 Hz, 1H),
.28 (ddd, J ) 14.5, 11.1, 3.4 Hz, 1H), 1.30 (s, 3H), 1.25 (s,
H), 1.15 (s, 3H); 13C NMR (100 MHz) δ 211.7, 140.9, 129.8,
oct-5-en -2-on e (1g). Following the procedure described for the
preparation of 1a , a mixture of 15g (374 mg, 1.11 mM), tri-
n-butylamine (615 mg, 3.32 mM), formic acid (155 mg, 3.37
3 2 2
mM), and Pd(PPh ) Cl (60 mg, 0.085 mM) in DMF (1 mL) was
used, and the residue was purified by column chromatography
on silica gel using 2.5% ethyl acetate in hexanes as an eluent
to obtain a yellowish oil 1g (159 mg, 75%); IR (neat) 2974,
716, 1380, 1031, 997, 910 cm ; H NMR (400 MHz) δ 6.51
dd, J ) 8.0, 6.4 Hz, 1H), 5.61 (ddd, J ) 8.0, 1.4, 1.4 Hz, 1H),
5.37 (ddd, J ) 17.0, 9.9, 9.1 Hz, 1H), 4.92 (dd, J ) 9.9, 1.6 Hz,
1H), 4.91 (ddd, J ) 17.0, 1.6, 0.8 Hz, 1H), 2.52-2.48 (m, 1H),
2.29 (ddd, J ) 12.5, 9.3, 3.0 Hz, 1H), 2.23 (ddd, J ) 9.3, 9.1,
5.2 Hz, 1H), 1.20 (ddd, J ) 12.5, 5.2, 2.7 Hz, 1H), 1.09 (s, 3H),
1.09 (s, 3H), 1.03 (s, 3H); 13C NMR (100 MHz) δ 217.0, 139.9,
138.4, 129.6, 115.2, 52.1, 44.4, 43.6, 43.3, 30.7, 27.7, 24.6, 16.1;
MS (EI) m/z (rel intensity) 190 (M , 29), 136 (35), 120 (100),
119 (40), 105 (44), 28 (20); HRMS (EI) calcd for C13
190.1358, found 190.1356.
0.1, 52.4, 44.8, 43.1, 29.1, 28.7, 23.1, 14.7; MS (FAB) m/z (rel
+
intensity) 210 (M , 64), 137 (30), 130 (28), 128 (52), 93 (100),
9
NO
1 (35), 55 (30), 43 (35), 41 (29); HRMS (EI) calcd for C11
H
15
-
-1
1
1
(
+
3
(M ) 209.1052, found 209.1038.
(
1S*,4S*,7R*)-1,3,3-Tr im eth yl-7-n itr obicyclo[2.2.2]oct-
5
1
-en -2-on e (1d ′): IR (neat) 2975, 2935, 1726, 1553, 1366,
-
1 1
352, 1035 cm ; H NMR (400 MHz) δ 6.70 (dd, J ) 8.0, 7.4
Hz, 1H), 5.69 (d, J ) 8.0, 1H), 4.70 (dd, J ) 9.3, 5.8 Hz, 1H),
2
.75-2.71 (m, 1H), 2.66 (ddd, J ) 13.8, 9.3, 3.6 Hz, 1H), 2.07
(
(
ddd, J ) 13.8, 5.8, 2.6 Hz, 1H), 1.27 (s, 3H), 1.10 (s, 3H), 1.06
1
3
+
s, 3H); C NMR (100 MHz) δ 210.9, 138.4, 127.3, 85.3, 53.6,
+
4
2
3.1, 42.6, 30.8, 28.0, 24.3, 14.4; MS (FAB) m/z (rel intensity)
H
18O (M )
+
10 (M , 20), 154 (43), 137 (29), 136 (46), 130 (100), 128 (76),
J . Org. Chem, Vol. 69, No. 2, 2004 457