9878
Y. Nishihara et al. / Tetrahedron 62 (2006) 9872–9882
1
3
1
2
(
Hz, 1H, CHCN), 4.13 (m, 2H, OCH2); C{ H} NMR
CDCl , 75 MHz, rt): d 13.6 (CH CH CH CH ), 19.1
(m), 1267 (m), 1238 (m), 1201 (s), 1183 (m), 1156 (m),
1110 (m), 1038 (m), 959 (w), 849 (w), 756 (w). H NMR
1
3
2
2
2
3
(
3
CH CH CH CH ), 27.7 (CH CH CH CH ), 28.3 (CH ),
2
(CDCl , 300 MHz, rt): d 2.02 (d of quintet, J¼10 Hz, 2 Hz,
2
2
3
2
2
2
3
2
3
0.4 (CH ), 36.6 (CH +CHCN), 39.0 (bridgehead carbon
2
1H, one of methylene (anti)), 2.36 (dt, J¼11 Hz, 2 Hz, 1H,
one of methylene (syn)), 2.73 (dd, J¼10 Hz, 2 Hz, 1H,
CHCOOEt), 2.85 (dd, J¼10 Hz, 2 Hz, 1H, CHCN), 3.72
(d, J¼6 Hz, 2H, 2 bridgehead methine protons), 3.82 (s,
2
n
(
(
(
(
(
CN side)), 41.9 (bridgehead carbon (COO Bu side)), 50.1
CHCOO Bu), 65.1 (OCH ), 119.8 (CN), 171.4 (CO). MS
El, m/z (relative intensity)): 221 (M , 1), 179 (7), 166
100), 154 (31), 148 (43), 120 (95), 104 (4), 98 (53), 93
32), 80 (12), 77 (11), 72 (5), 66 (39). Anal. Calcd for
n
2
+
1
3
1
3H, OCH ), 7.11–7.27 (m, 4H, aromatics); C{ H} NMR
3
(CDCl , 75 MHz, rt): d 34.9 (CHCN), 46.3 (bridgehead car-
3
C H NO : C, 70.56; H, 8.65; N, 6.33%. Found: C, 70.49;
1
bon (CN side)), 47.2 (CH ), 48.9 (CHCOOMe), 49.1 (bridge-
2
3
19
2
H, 8.76; N, 6.27%.
head carbon (COOMe side)), 52.5 (OCH ), 119.8 (CN),
3
1
21.3, 121.8, 126.9, 127.5, 144.5, 146.0, 172.0 (CO). MS
+
4
.4.6. (2R*,3S*)-Benzyl 3-cyanobicyclo[2.2.1]heptane-2-
(El, m/z (relative intensity)): 227 (M , 5), 196 (2), 167 (5),
141 (6), 128 (3), 116 (100), 102 (1), 89 (3), 80 (5), 63 (4),
51 (3). Anal. Calcd for C H NO : C, 73.99; H, 5.77; N,
carboxylate (3g). Off-white solid. R ¼0.57 (hexane/ethyl
f
ꢀ
yield was 14%. IR (KBr, cm ): 2967 (s), 2877 (m), 2235
acetate¼7/3). Mp¼75–76 C. GC yield was 31%. Isolated
1
4
13
2
ꢁ
1
6.16%. Found: C, 73.74; H, 5.71; N, 6.02%.
(
1
(
s, nCN), 1731 (s, nCO), 1454 (m), 1383 (s), 1350 (m),
302 (m), 1288 (m), 1222 (m), 1190 (s), 1167 (m), 1117
m), 1029 (m). H NMR (CDCl , 300 MHz, rt): d 1.21–
3
4.4.9. (2R*,3S*)-n-Propyl 1,2,3,4-tetrahydro-3-cyano-
1,4-methanonaphthalene-2-carboxylate (5c). A colorless
1
1
2
.25 (m, 2H, ethylene CH (endo)), 1.45 (dt, J¼11 Hz,
oil. R ¼0.72 (hexane/ethyl acetate¼7/3). GC yield was
f
ꢁ
1
Hz, 1H, one of methylene (anti)), 1.59–1.67 (m, 2H, ethyl-
83%. Isolated yield was 76%. IR (neat, cm ): 2970 (s),
2882 (s), 2238 (m, nCN), 1733 (s, nCO), 1470 (m), 1393
ene CH (exo)), 1.95 (dt, J¼11 Hz, 2 Hz, 1H, one of methyl-
ene (syn)), 2.62–2.65 (m, 3H, 2 bridgehead methine
protons+CHCOOBn), 2.85 (dd, J¼10 Hz, 2 Hz, 1H,
(m), 1352 (m), 1308 (s), 1265 (m), 1237 (m), 1194 (m),
1185 (m), 1109 (s). H NMR (CDCl , 300 MHz, rt): d 0.97
1
3
CHCN), 5.10 (d, J¼12 Hz, 1H, OCH ), 5.23 (d, J¼12 Hz,
(td, J¼8 Hz, 1 Hz, 3H, CH CH CH ), 1.72 (td, J¼8 Hz,
2
2
2
3
1
3
1
1
H, OCH ), 7.33–7.43 (m, 5H, aromatics); C{ H} NMR
2
1 Hz, 2H, CH CH CH ), 2.01 (dd, 1H, one of methylene
2 2 3
(
(
(
6
(
(
CDCl , 75 MHz, rt): d 27.7 (CH ), 28.2 (CH ), 36.7
3
CH +CHCN), 39.0 (bridgehead carbon (CN side)), 41.9
2
(anti)), 2.36 (dd, J¼10 Hz, 2 Hz, 1H, one of methylene
2
2
n
(syn)), 2.70 (d, J¼10 Hz, 1H, CHCOO Pr), 2.85 (d,
bridgehead carbon (COOBn side)), 50.2 (CHCOOBn),
7.2 (OCH ), 119.9 (CN), 128.4, 128.5, 128.7, 135.3, 171.2
J¼10 Hz, 1H, CHCN), 3.72 (d, J¼8 Hz, 2H, 2 bridgehead
methine protons), 4.17 (t, J¼8 Hz, 2H, OCH ), 7.10–7.26
2
2
+
13
1
CO). MS (El, m/z (relative intensity)): 255 (M , 13), 237
2), 227 (4), 148 (7), 120 (27), 107 (42), 91 (100), 79 (7),
(m, 4H, aromatics); C{ H} NMR (CDCl , 75 MHz, rt):
3
d 10.4 (CH CH CH ), 21.8 (CH CH CH ), 34.9 (CHCN),
2
2
3
2
2
3
7
6
7 (8), 66 (19). Anal. Calcd for C H NO : C, 75.27; H,
1
.71; N, 5.49%. Found: C, 74.87; H, 6.60; N, 5.10%.
46.3 (bridgehead carbon (CN side)), 47.2 (CH ), 48.9
2
6
17
2
n
n
(bridgehead carbon (COO Pr side), 49.0 (CHCOO Pr),
7.2 (OCH ), 119.8 (CN), 121.3, 121.8, 126.8, 127.4,
144.5, 146.1, 171.6 (CO). MS (El, m/z (relative intensity)):
6
2
4.4.7. (2R*,3S*)-Ethyl 1,2,3,4-tetrahydro-3-cyano-1,4-
methanonaphthalene-2-carboxylate (5a). White solid.
+
255 (M , 5), 196 (3), 168 (8), 153 (2), 141 (8), 128 (4), 116
ꢀ
IR (KBr, cm ): 2979 (s), 2886 (m), 2240 (s, nCN), 1739
Mp 66–67 C. GC yield was 99%. Isolated yield was 83%.
(100), 98 (14), 89 (2), 80 (3), 65 (2). Anal. Calcd for
C H NO : C, 75.27; H, 6.71; N, 5.49%. Found: C, 75.32;
H, 6.67; N, 5.21%.
ꢁ
1
1
6
17
2
(
(
s, nCO), 1468 (m), 1374 (m), 1347 (m), 1312 (m), 1264
m), 1240 (m), 1181 (s), 1156 (m), 1107 (m), 1036 (m),
1
9
51 (w), 857 (w), 754 (w). H NMR (CDCl , 300 MHz, rt):
3
4.4.10. (2R*,3S*)-iso-Propyl 1,2,3,4-tetrahydro-3-cyano-
1,4-methanonaphthalene-2-carboxylate (5d). White solid.
d 1.33 (t, J¼7 Hz, 3H, CH ), 2.02 (d of quintet, J¼10 Hz,
3
ꢀ
yield was 83%. Isolated yield was 68%. IR (KBr, cm ):
2
1
Hz, 1H, one of methylene (anti)), 2.36 (dt, J¼10 Hz, 2 Hz,
H, one of methylene (syn)), 2.70 (dd, J¼10 Hz, 2 Hz, 1H,
R ¼0.71 (hexane/ethyl acetate¼7/3). Mp 90–91 C. GC
f
ꢁ
1
CHCOOEt), 2.85 (dd, J¼9 Hz, 2 Hz, 1H, CHCN), 3.72 (d,
J¼7 Hz, 2H, 2 bridgehead methine protons), 4.28 (qd,
2986 (m), 2977 (m), 2239 (s, nCN), 1724 (s, nCO), 1473
(m), 1461 (s), 1366 (m), 1304 (s), 1237 (m), 1202 (m),
1
J¼7 Hz, 4 Hz, 2H, OCH ), 7.11–7.27 (m, 4H, aromatics);
1104 (s), 1020 (m). H NMR (CDCl , 300 MHz, rt): d 1.30
3
2
1
3
1
C{ H} NMR (CDCl , 75 MHz, rt): d 14.1 (CH ), 34.9
3
(d, J¼6 Hz, 3H, CH ), 1.34 (d, J¼6 Hz, 3H, CH ), 2.01
3
3
3
(
4
(
CHCN), 46.5 (bridgehead carbon (CN side)), 47.1 (CH2),
8.8 (bridgehead carbon (COOEt side)+CHCOOEt), 61.6
OCH ), 119.7 (CN), 121.2, 121.7, 126.7, 127.3, 144.4,
(dd, J¼10 Hz, 2 Hz, 1H, one of methylene (anti)), 2.35
(dd, J¼10 Hz, 2 Hz, 1H, one of methylene (syn)), 2.64 (dd,
i
J¼10 Hz, 2 Hz, 1H, CHCOO Pr), 2.84 (dd, J¼10 Hz, 2 Hz,
2
1
46.0, 171.5 (CO). MS (El, m/z (relative intensity)): 241
1H, CHCN), 3.71 (d, J¼10 Hz, 2H, 2 bridgehead methine
protons), 5.15 (sep, J¼6 Hz, 1H, OCH), 7.10–7.26 (m, 4H,
+
(
M , 4), 196 (2), 167 (6), 141 (7), 126 (5), 116 (100), 98
10), 89 (3), 80 (5), 63 (4), 51 (3). Anal. Calcd for
1
3
1
(
C H NO : C, 74.67; H, 6.27; N, 5.80%. Found: C, 74.48;
H, 6.24; N, 5.63%.
aromatics); C{ H} NMR (CDCl , 75 MHz, rt): d 21.7
3
(CH ), 21.9 (CH ), 34.9 (CHCN), 46.4 (bridgehead carbon
3
1
5
15
2
3
i
(CN side)), 47.2 (CH ), 48.8 (bridgehead carbon (COO Pr
2
i
side)), 49.0 (CHCOO Pr), 69.4 (OCH), 119.8 (CN), 121.2,
121.8, 126.8, 127.4, 144.5, 146.2, 171.1 (CO). MS (El, m/z
(relative intensity)): 255 (M , 6), 213 (2), 196 (6), 168 (14),
4.4.8. (2R*,3S*)-Methyl 1,2,3,4-tetrahydro-3-cyano-1,4-
methanonaphthalene-2-carboxylate (5b). A colorless liq-
+
ꢀ
was 65%. IR (neat, cm ): 3024 (m), 2956 (m), 2242 (m,
nCN), 1740 (s, nCO), 1462 (m), 1437 (m), 1352 (m), 1311
uid. Bp 75 C/1.8 Torr. GC yield was 74%. Isolated yield
153 (2), 140 (10), 128 (5), 116 (100), 98 (17), 89 (3), 80
(3), 63 (2). Anal. Calcd for C H NO : C, 75.27; H, 6.71;
N, 5.49%. Found: C, 75.00; H, 6.73; N, 5.23%.
ꢁ
1
1
6
17
2