The Journal of Organic Chemistry
Article
(
d, J = 15.9 Hz, 1H), 6.84 (d, J = 8.8 Hz, 2H), 7.31 (d, J = 8.8 Hz,
128.3, 129.0, 129.1, 129.1, 130.5, 132.4, 138.4 ppm; IR (KBr) ν 2227
−1
2
1
1
H), 7.53−7.70 (m, 3H), 7.84 (d, J = 7.3 Hz, 1H), 8.10 (d, J = 8.3 Hz,
(CN) cm ; MS (EI+) m/z (relative intensity) 91 (100), 145 (87),
+
H), 8.23 (d, J = 7.5 Hz, 1H) ppm; MS (EI+) m/z (relative intensity)
313 (1, M ). Anal. Calcd for C H NO: C, 84.32; H, 6.11; N, 4.47.
22
19
+
35 (100), 166 (31), 329 (16, M ). Simmons−Smith reaction of this
Found: C, 84.27; H, 6.07; N, 4.51.
alkene was carried out under similar conditions described in the
preparation of 4a. Purification by recrystallization from hexane-EtOH
gave pure 4-(trans-2-p-methoxyphenylcyclopropyl)methoxymethyl-1-
(1S*,4aR*,10bR*,11S*)-10b-Cyano-11-p-methoxyphenyl-
1
,2,4,10b-tetrahydro-4a,1-ethanobenzo[f ]isochromene (exo-3b).
1
Colorless solid: mp 125−128 °C; H NMR (300 MHz, CDCl ) δ
3
1
2
3
1
.24 (m, 2H), 3.06 (m, 2H), 3.51 (d, J = 11.8 Hz, 1H), 3.78 (s, 3H),
.96 (d, J = 11.9 Hz, 1H), 4.07 (dd, J = 11.5, 2.8 Hz, 1H), 4.37 (d, J =
1.3 Hz, 1H), 5.48 (d, J = 9.5 Hz, 1H), 6.69 (d, J = 9.6 Hz, 1H), 6.81
naphthonitrile (4b). Colorless needles: mp 197−198 °C; H NMR
(
300 MHz, CDCl ) δ 0.91 (m, 2H), 1.40 (m, 1H), 1.78 (m, 1H), 3.58
3
(
2
2
d, J = 6.7 Hz, 2H), 3.75 (s, 3H), 5.00 (s, 2H), 6.78 (d, J = 8.7 Hz,
(
d, J = 8.8 Hz, 2H), 7.32 (d, J = 8.7 Hz, 2H), 7.26−7.46 (m, 4H) ppm;
H), 6.97 (d, J = 8.8 Hz, 2H), 7.57 (d, J = 7.4 Hz, 1H), 7.57−7.68 (m,
1
3
C NMR (75 MHz, CDCl ) δ 32.5, 41.6, 48.3, 50.6, 51.3, 55.4, 68.9,
H), 7.82 (d, J = 7.4 Hz, 1H), 8.10 (d, J = 8.4 Hz, 1H), 8.22 (d, J = 8.2
3
13
Hz, 1H) ppm; C NMR (75 MHz, CDCl ) δ 13.8, 21.2, 22.2, 55.4,
7
1
cm ; MS (EI+) m/z (relative intensity) 147 (100), 166 (36), 343 (12,
M ); HRMS (EI+) Calcd for C H NO : 343.1572, Found: 343.1575.
71.2, 113.5, 119.5, 123.9, 127.9, 128.3, 129.0, 129.0, 130.0, 130.4,
3
−1
0.3, 74.5, 110.1, 113.8, 117.8, 124.3, 124.3, 125.7, 126.8, 127.5, 128.2,
130.6, 130.6, 132.4, 158.4 ppm; IR (KBr) ν 2226 (CN) cm ; MS (EI
+
+
) m/z (relative intensity) 135 (66), 147 (100), 343 (8, M ); HRMS
30.8, 132.0, 132.2, 134.1, 140.1, 157.6 ppm; IR (KBr) ν 2222 (CN)
−1
(
EI+) Calcd for C H NO : 343.1572, Found: 343.1565.
23 21
2
+
(
3aS*,5S*,6R*,10bS*)-6-Cyano-5-phenyl-1,3,3a,4,5,6-hexahy-
23
21
2
dro-6,10b-ethenobenzo[3,4]cyclohepta[1,2-c]furan (5a). Colorless
blocks: mp 226−227 °C; H NMR (300 MHz, CDCl ) δ 1.09 (m,
Photoreaction. A benzene, CH Cl or CH CN solution (10 mL),
2
2
3
1
containing 1 or 4 (10 mM), in cylindrical Pyrex vessels (ϕ = 8 mm)
was purged with argon for 15 min and then the vessel was sealed. The
solution was irradiated by using a 300 W high pressure mercury lamp
at room temperature (>280 nm light). The temperature of the solution
during irradiation was maintained around room temperature by using
circulated cooling water.
3
1
4
1
7
4
1
H), 1.87 (m, 1H), 2.46 (m, 1H), 3.13−3.24 (m, 2H), 4.01 (m, 1H),
.03 (d, J = 9.6 Hz, 1H), 4.67 (d, J = 9.3 Hz, 1H), 6.40 (d, J = 8.5 Hz,
H), 6.67 (d, J = 8.5 Hz, 1H), 6.98 (m, 2H), 7.26−7.34 (m, 3H),
1
3
.38−7.56 (m, 4H) ppm; C NMR (75 MHz, CDCl ) δ 34.5, 42.9,
3
5.5, 49.4, 50.6, 73.5, 75.2, 120.4, 124.0, 126.0, 126.8, 127.9, 128.1,
28.6, 128.8, 133.5, 135.2, 136.7, 138.1, 141.9 ppm; IR (KBr) ν 2240
(
1S*,2aS*,5aS*,11bS*)-11b-Cyano-1-phenyl-1,2,2a,3,5,11b-
−1
(CN) cm ; MS (EI+) m/z (relative intensity) 91 (100), 117 (81),
hexahydrobenzo[4,5]indeno[1,7a-c]furan (2a). Colorless blocks: mp
+
1
313 (12, M ); HRMS (EI+) Calcd for C H NO: 313.1467, Found:
1
1
1
9
1
5
1
2
88−191 °C; H NMR (300 MHz, CDCl ) δ 2.30 (m, 2H), 2.90 (m,
22 19
3
3
13.1470.
3aS*,5S*,6R*,10bS*)-6-Cyano-5-p-methoxyphenyl-1,3,3a,4,5,6-
hexahydro-6,10b-ethenobenzo[3,4]cyclohepta[1,2-c]furan (5b).
H), 3.24 (m, 1H), 3.42 (d, J = 10.4 Hz, 1H), 3.96 (m, 1H), 4.05 (m,
H), 4.31 (d, J = 10.3 Hz, 1H), 5.71 (d, J = 9.8 Hz, 1H), 6.45 (d, J =
.8 Hz, 1H), 6.59 (d, J = 7.6 Hz, 1H), 6.89−7.01 (m, 3H), 7.14 (m,
(
1
13
White solid: mp 181−183 °C; H NMR (300 MHz, CDCl
3
) δ 1.04
H), 7.18−7.31 (m, 4H) ppm; C NMR (75 MHz, CDCl ) δ 33.9,
3
(
m, 1H), 1.84 (m, 1H), 2.45 (m, 1H), 3.12−3.20 (m, 2H), 3.79 (s,
H), 4.01 (m, 2H), 4.66 (d, J = 9.3 Hz, 1H), 6.39 (d, J = 8.7 Hz, 1H),
2.6, 57.5, 58.1, 60.4, 74.1, 75.5, 119.4, 124.1, 127.2, 127.3, 127.8,
3
27.9, 128.5, 129.1, 129.2, 129.2, 129.4, 130.8, 135.2 ppm; IR (KBr) ν
−1
6.66 (d, J = 8.5 Hz, 1H), 6.82 (d, J = 8.6 Hz, 2H), 6.90 (d, J = 8.6 Hz,
234 (CN) cm ; MS (EI+) m/z (relative intensity) 117 (66), 179
1
3
+
2H), 7.38−7.53 (m, 4H) ppm; C NMR (75 MHz, CDCl
3
) δ 34.6,
3.1, 44.6, 49.8, 50.6, 55.4, 73.5, 75.2, 113.9, 120.5, 123.9, 125.9, 126.8,
28.1, 129.0, 133.5, 134.1, 135.1, 136.6, 138.0, 159.0 ppm; IR (KBr) ν
(
100), 313 (46, M ). Anal. Calcd for C H NO: C, 84.32; H, 6.11; N,
22 19
4
1
2
4
.47. Found: C, 84.08; H, 6.14; N, 4.41.
(
1S*,4aR*,10bR*,11R*)-10b-Cyano-11-phenyl-1,2,4,10b-tetrahy-
−1
244 (CN) cm ; MS (EI+) m/z (relative intensity) 134 (74), 147
(100), 343 (18, M ); HRMS (EI+) Calcd for C23
dro-4a,1-ethanobenzo[f ]isochromene (endo-3a). Colorless blocks:
+
1
H21NO : 343.1572,
2
mp 203−204 °C; H NMR (300 MHz, CDCl ) δ 2.32 (m, 2H), 3.17
3
Found: 343.1568.
(
m, 1H), 3.72 (m, 1H), 3.82 (d, J = 11.3 Hz, 1H), 4.03 (dd, J = 11.6,
trans-(1(12)Z,8E)-9-Cyano-7-phenyl-4,5,6,7-tetrahydro-2H-1,5-
2
(
6
7
4
1
.7 Hz, 1H), 4.25 (d, J = 11.3 Hz, 1H), 4.34 (d, J = 11.7 Hz, 1H), 5.35
d, J = 9.6 Hz, 1H), 6.18 (d, J = 9.6 Hz, 1H), 6.23 (d, J = 7.3 Hz, 2H),
.79 (d, J = 7.4 Hz, 1H), 6.87 (m, 2H), 6.97 (m, 1H), 7.27 (m, 1H),
(
metheno)benzo[d][1]oxacycloundecin (6a). Colorless blocks: mp
1
1
1
4
7
47−148 °C; H NMR (300 MHz, CDCl ) δ 2.19 (m, 1H), 2.33 (m,
3
H), 2.81 (m, 1H), 3.58 (m, 1H), 3.74 (m, 1H), 4.10−4.19 (m, 2H),
.34 (m, 1H), 5.87 (m, 1H), 6.69 (d, J = 11.4 Hz, 1H), 7.10 (m, 2H),
.20−7.34 (m, 4H), 7.34−7.40 (m, 3H) ppm; C NMR (75 MHz,
CDCl ) δ 33.1, 41.3, 45.9, 68.9, 70.3, 110.8, 120.5, 125.8, 127.3, 127.4,
1
3
.34−7.46 (m, 2H) ppm; C NMR (75 MHz, CDCl ) δ 34.0, 42.6,
3
9.5, 51.5, 51.7, 70.7, 75.5, 120.0, 123.4, 126.1, 126.6, 127.1, 127.9,
13
28.6, 128.9, 129.1, 129.2, 129.9, 134.9, 140.5 ppm; IR (KBr) ν 2224
−1
3
(
CN) cm ; MS (EI+) m/z (relative intensity) 91 (89), 146 (100),
1
27.9, 129.0, 129.4, 129.5, 132.9, 133.4, 138.0, 139.7, 141.8, 154.0
+
3
3
13 (2, M ); HRMS (EI+) Calcd for C H NO: 313.1467, Found:
−1
22
19
ppm; IR (KBr) ν 2212 (CN) cm ; MS (EI+) m/z (relative intensity)
13.1468.
1S*,4aR*,10bR*,11R*)-10b-Cyano-11-p-methoxyphenyl-
,2,4,10b-tetrahydro-4a,1-ethanobenzo[f ]isochromene (endo-3b).
+
9
1 (100), 146 (98), 179 (97), 313 (45, M ). Anal. Calcd for
(
C H NO: C, 84.32; H, 6.11; N, 4.47. Found: C, 83.94; H, 6.14; N,
22
19
1
4
.43.
1
Colorless solid: mp 146−148 °C; H NMR (300 MHz, CDCl ) δ
3
2
3
1
.21 (m, 1H), 2.35 (m, 1H), 3.15 (m, 1H), 3.67 (m, 1H), 3.68 (s, 3H),
.80 (d, J = 11.3 Hz, 1H), 4.02 (dd, J = 11.5, 2.6 Hz, 1H), 4.24 (d, J =
1.3 Hz, 1H), 4.32 (d, J = 11.7 Hz, 1H), 5.34 (d, J = 9.6 Hz, 1H), 6.13
ASSOCIATED CONTENT
Supporting Information
■
*
S
(
d, J = 8.8 Hz, 2H), 6.22 (d, J = 9.6 Hz, 1H), 6.42 (d, J = 8.8 Hz, 2H),
13
6
.83 (d, J = 7.2 Hz, 1H), 7.28 (m, 1H), 7.34−7.45 (m, 2H) ppm; C
NMR (75 MHz, CDCl ) δ 34.5, 42.5, 49.4, 50.8, 51.6, 55.3, 70.7, 75.4,
1
1
3
12.6, 120.0, 123.4, 126.7, 127.9, 128.8, 129.0, 129.2, 129.5, 129.9,
CIF files for 2a, endo-3a, exo-3a, 5a, and 6a (ZIP)
NMR spectra for compounds: 1a,b; 2a; endo-3a,b; exo-
−1
32.6, 134.9, 157.7 ppm; IR (KBr) ν 2228 (CN) cm ; MS (EI+) m/z
+
(
relative intensity) 135 (56), 147 (100), 343 (10, M ); HRMS (EI+)
3
a,b; 4a,b; 5a,b; and 6a, description of X-ray crystallo-
graphic analysis including full-page size ORTEP plots
Calcd for C H NO : 343.1572, Found: 343.1578.
23
21
2
(
1S*,4aR*,10bR*,11S*)-10b-Cyano-11-phenyl-1,2,4,10b-tetrahy-
dro-4a,1-ethanobenzo[f ]isochromene (exo-3a). Colorless blocks:
1
mp 150−153 °C; H NMR (300 MHz, CDCl ) δ 2.19 (m, 1H), 2.34
3
(
m, 1H), 3.10 (m, 2H), 3.49 (d, J = 11.8 Hz, 1H), 3.96 (d, J = 11.9 Hz,
AUTHOR INFORMATION
1
H), 4.08 (dd, J = 11.5, 2.9 Hz, 1H), 4.37 (d, J = 11.5 Hz, 1H), 5.49
(
7
d, J = 9.8 Hz, 1H), 6.70 (d, J = 9.6 Hz, 1H), 7.19−7.32 (m, 4H),
1
3
.32−7.48 (m, 5H) ppm; C NMR (75 MHz, CDCl ) δ 32.1, 41.7,
3
4
9.0, 50.7, 51.4, 68.9, 71.2, 119.5, 123.9, 126.9, 128.0, 128.1, 128.1,
G
J. Org. Chem. XXXX, XXX, XXX−XXX