Unusual Reactions of Halo[5]metacyclophanes
FULL PAPER
H), 3.77 (s, 3 H, OMe), 3.76 (s, 3 H, OMe), 2.7Ϫ2.3 (m, 4 H, 4-,8-
77.7, 128.7 (d), 129.8 (d), 154.2 (s), 157.4 (s), signal of CN missing
H), 2.3Ϫ1.5 (m, 4 H, 6-H and 5-,7-Hexo), 1.0Ϫ0.8 (m, 2 H, 5-,7- due to low intensity.
Hendo). MS: m/z (%) ϭ 322 (10) [Mϩ·], 291 (14), 180 (23), 167 (28),
145 (53), 125 (100), 91 (71). HRMS (C17H19ClO4): calcd. 322.0972;
found 322.0972.
Reaction with 1c: Ratio 8c/9c ϭ 15:85. MS: m/z (%) ϭ 267 (10)
[Mϩ·], 232 (100) [Mϩ· Ϫ Cl], 214 (12), 196 (20), [Mϩ· Ϫ HCl, Ϫ Cl],
179 (28), 115 (29). HRMS (C14H15Cl2N): calcd. 267.0582; found
267.0579. 1,10-Dichloro-11-cyanotricyclo[7.3.1.03,10]trideca-2,9(13)-
Reaction with 1d. ؊ Dimethyl 10-Fluorotricyclo[7.3.1.03,10]trideca-
2,9(13)-diene-11,12-dicarboxylate (7d): 1H NMR (200 MHz): δ ϭ
1
4
diene (8c): H NMR (400 MHz): δ ϭ 6.20 (d, J ϭ 1.1 Hz, 1 H),
4
3
3
3
6.22 (dd, 3J ϭ 5.8 Hz, JH,F ϭ 6.0 Hz, 2 H, 2-,13-H), 5.04 (td, J ϭ
6.14 (d, J ϭ 1.1 Hz, 1 H), 3.22 (dd, J ϭ 10.5, J ϭ 4.4 Hz, 1 H,
11-H), 2.8Ϫ2.7 (m, 2 H, 4-,8-Hexo), 2.56 [AB system: δA ϭ 2.62
5.8 Hz, JH,F ϭ 1.2 Hz, 1 H, 1-H), 3.87 (s, 3 H, OMe), 3.86 (s, 3 H,
OMe), 2.7Ϫ2.3 (m, 4 H, 4-,8-H), 2.3Ϫ1.5 (m, 4 H, 6-H and 5-,7-
Hexo), 1.0Ϫ0.8 (m, 2 H, 5-,7-Hendo). MS: m/z (%) ϭ 306 (93)
[Mϩ·], 293 (77), 247 (60), 207 (91), 194 (100). HRMS (C17H19FO4):
calcd. 306.1267; found 306.1266.
2
3
4
(ddd, J ϭ Ϫ11.2, J ϭ 10.5, J ϭ 1.1 Hz, 1 H, 12-Hanti), δB ϭ
2.45 (ddd, 2J ϭ Ϫ12.5, 3J ϭ 4.4, 4J ϭ 1.1 Hz, 1 H, 12-Hsyn)],
2.4Ϫ1.0 (m, 8 H). 13C NMR (50.3 MHz): δ ϭ 23.7 (C-6), 32.3 (C-
4,-8), 36.7 (C-5,-7), 41.3 (d, C-11), 42.4 (t, C-12), 64 (s), 74 (s),
120 (CN), 132.9 (d), 134.0 (d), 153 (s), 153.5 (s). 1,10-Dichloro-12-
cyanotricyclo[7.3.1.03,10]trideca-2,9(13)-diene (9c): 1H NMR
Acrylonitrile Adducts: In all cases, a mixture of regioisomers 8 and
9 was obtained. No efforts were made to separate them.
4
(400 MHz): δ ϭ 6.10 (d, J ϭ 1.0 Hz, 1 H, 2-H), 5.99 (s, 1 H, 13-
3
3
4
H), 3.27 (ddd, J ϭ 10.5, J ϭ 4.4, J ϭ 1.0 Hz, 1 H, 12-H), 2.78
Reaction with 1a: Ratio 8a/9a ϭ 9:91. MS: m/z (%) ϭ 199 (32)
[Mϩ·], 146 (77), 131 (93), 117 (85), 115 (76), 104 (100), 91 (90), 84
(79), 77 (38). HRMS (C14H17N): calcd. 199.1361; found 199.1362.
11-Cyanotricyclo[7.3.1. 03,10]trideca-2,9(13)-diene (8a): 1H NMR
(400 MHz): δ ϭ 6.12 (d, 1 H), 6.07 (d, 1 H), 3.61 (m, 1 H, 1-H),
3.59 (m, 1 H, 10-H), 2.61 (ddd, 1 H, 11-H), 2.5Ϫ0.8 (m, 12 H). 12-
Cyanotricyclo[7.3.1.03,10]trideca-2,9(13)-diene (9a): 1H NMR
(ddd, 2J ϭ Ϫ13.3, J ϭ 11.7, 3J ϭ 4.0 Hz, 1 H, 8- or 4-Hexo), 2.74
3
(ddd, 2J ϭ Ϫ13.3, 3J ϭ 12.0, 3J ϭ 4.5 Hz, 1 H, 4- or 8-Hexo), 2.48
[AB system: δA ϭ 2.55 (dd, 2J ϭ Ϫ12.5, 3J ϭ 10.5 Hz, 1 H,
11Hanti), δB ϭ 2.40 (dd, 2J ϭ Ϫ12.5, 3J ϭ 4.6 Hz, 1 H, 11-Hsyn)],
2.45Ϫ2.35 (m, 2 H, 4-,8-Hendo), 2.24 (m, 2 H, 5-,7-Hexo), 2.00 (dt,
3
2
3
2J ϭ Ϫ16.1, J ϭ 10.7 Hz, 1 H, 6-H), 1.73 (dt, J ϭ Ϫ16.1, J ϭ
9.0 Hz, 1 H, 6-H), 1.03 (m,
2
H, 5-,7-Hendo). 13C NMR
3
3
(400 MHz): δ ϭ 5.94 (d, J ϭ 5.6 Hz, 1 H), 5.81 (d, J ϭ 5.8 Hz,
(50.3 MHz): δ ϭ 23.8 (C-6), 32.2 (C-4 or C-8), 32.3 (C-4 or C-8),
36.8 (C-5 or C-7), 36.9 (C-5 or C-7), 39.4 (d, C-12), 43.8 (t, C-11),
65.7 (s), 72.3 (s), 119.2 (CN), 129.7 (d, C-13), 130.2 (d, C-2), 157.6
(s), 158.9 (s).
3
3
3
1 H), 3.83 (ddd, J ϭ 5.8, J ϭ 5.6, J ϭ 2.7 Hz, 1 H, 1-H), 3.37
4
3
3
(m, several J unresolved, 1 H, 10-H), 2.75 (ddd, J ϭ 10.3, J ϭ
4.6, 3J ϭ 2.7 Hz, 1 H, 12-H), 2.44 (ddd, 2J ϭ Ϫ12.3, 3J ϭ 3J ϭ
4.2 Hz, 1 H, 8- or 4-Hendo), 2.35 (ddd, 2J ϭ Ϫ12.3, 3J ϭ 3J ϭ
4.2 Hz, 1 H, 4- or 8-Hendo), 2.26Ϫ2.11 (m, 4 H, 4,8-Hexo, 5,7-
Reaction with 1d: Ratio 8d/9d ϭ 15:85. MS: m/z (%) ϭ 217 (93)
[Mϩ·], 176 (52), 164 (58), 149 (60), 135 (75), 122 (100), 109 (40).
11-Cyano-10-fluorotricyclo[7.3.1.03,10]trideca-2,9(13)-diene (8d): 1H
2
3
3
Hexo), 1.90 (ddd, J ϭ Ϫ15.8, J ϭ J ϭ 9.5 Hz, 1 H, 6-H), 1.77
2
3
3
[AB system: δA ϭ 1.87 (ddd, J ϭ Ϫ12.7, J ϭ 10.3, J ϭ 2.6 Hz,
1 H, 11-Hanti), δB ϭ 1.67 (ddd, 2J ϭ Ϫ12.7, 3J ϭ 4.6, 3J ϭ 2.5 Hz,
3
NMR (400 MHz): δ ϭ 5.99 (t, J ϭ JH,F ϭ 5.9 Hz, 1 H), 5.91 (t,
2
3
3
3
3
3
1 H, 11-Hsyn)], 1.56 (ddd, J ϭ Ϫ15.8, J ϭ J ϭ 9.8 Hz, 1 H, 6-
H), 1.10Ϫ 0.99 (m, 2 H, 5-,7-Hendo). 13C NMR (50.3 MHz): δ ϭ
25.1, 27.2, 29.1, 35.0, 35.1, 35.2, 35.2, 40.7 (d), 46.7 (d), 124.5 (d),
125.2 (d), 156.8 (s), 157.4 (s).
JH,F ϭ J ϭ 5.9 Hz, 1 H), 3.60 (tt, J ϭ 5.9, J ϭ 2.8 Hz, 1 H, 1-
H), 2.90 (ddd, 3J ϭ 10.6, 3J ϭ 4.7 Hz, JH,F ϭ 4.4 Hz, 1 H, 11-
H), 2.6Ϫ1.5 (m, 10 H), 1.0Ϫ0.8 (m, 2 H, 5-,7-Hendo). 13C NMR
(50.3 MHz): δ ϭ 25.0 (JC,F ϭ 7 Hz!, C-6), 30.7, 31.4, 32.4 (JC,F
ϭ
21 Hz, C-11), 36.7, 126.6 (JC,F ϭ 5 Hz), 127.1 (JC,F ϭ 5 Hz), 152.8
(JC,F ϭ 13 Hz), 152.8 (JC,F ϭ 13 Hz), signals of CN and C-10 miss-
ing due to low intensity. 19F NMR (376.43 MHz): δ ϭ Ϫ11.8. 12-
Cyano-10-fluorotricyclo[7.3.1.03,10]trideca-2,9(13)-diene (9d): 1H
Reaction with 1b: Ratio 8b/9b ϭ 44:56. MS: m/z (%) ϭ 233 (79)
[Mϩ·], 198 (88), 156 (55), 145 (100), 115 (70), 103 (50). HRMS
(C14H16ClN): calcd: 233.0971; found 233.0977. 10-Chloro-11-cyan-
otricyclo[7.3.1.03,10]trideca-2,9(13)-diene (8b): 1H NMR (400 MHz):
δ ϭ 6.13 (d, 3J ϭ 5.9 Hz, 1 H), 6.09 (d, 3J ϭ 5.9 Hz, 1 H), 3.62
(tt, 3J ϭ 5.9, 3J ϭ 2.9 Hz, 1 H, 1-H), 3.08 (dd, 3J ϭ 10.5, 3J ϭ
4.6 Hz, 1 H, 11-H), 2.8Ϫ2.6 (m, 2 H, 4-,8-Hexo), 2.4Ϫ2.3 (m, 2 H,
4-,8-Hendo), 2.2Ϫ2.1 (m, 2 H, 5-,7-Hexo), 2.14 [AB system: δA ϭ
3
NMR (400 MHz): δ ϭ 5.89 (dd, J ϭ 5.9 Hz, JH,F ϭ 5.9 Hz, 1 H,
2-H), 5.75 (dd, JH,F ϭ 5.9, 3J ϭ 5.8 Hz, 1 H, 13-H), 3.81 (ddd,
3
3
3
3J ϭ 5.9, J ϭ 5.8, J ϭ 2.8 Hz, 1 H, 1-H), 2.84 (ddd, J ϭ 10.6,
3J ϭ 4.7, 3J ϭ 2.8 Hz, 1 H, 12-H), 2.6Ϫ2.2 (m, 4 H, 4,8-H], 2.2Ϫ2.1
(m, 2 H, 5-,7-Hexo), 2.02 [AB system: δA ϭ 2.12 (ddd, 2J ϭ Ϫ11.9,
3J ϭ 10.6 Hz, JH,F ϭ 4.7 Hz, 1 H, 11-Hanti), δB ϭ 1.92 (ddd, 2J ϭ
3
3
2.22 (dddd, 2J ϭ Ϫ12.5, J ϭ 10.5, J ϭ 2.9, 4J ϭ 0.8 Hz, 1 H, 12-
Hanti), δB ϭ 2.07 (dddd, 2J ϭ Ϫ12.5, 3J ϭ 4.6, 3J ϭ 2.9, 4J ϭ
3
Ϫ11.9, J ϭ 4.7 Hz, JH,F ϭ 4.7 Hz, 1 H, 11-Hsyn)], 1.72 [AB sys-
3
3
0.8 Hz, 1 H, 12-Hsyn)], 1.98 (ddd, 2J ϭ Ϫ15.9, J ϭ J ϭ 10.7 Hz,
tem: δA ϭ 1.78 (dtd, 2J ϭ Ϫ15.6, 3J ϭ 9.2 Hz, JH,F ϭ 5.5 Hz),
3
1 H, 6-H), 1.56 (ddd, 2J ϭ Ϫ15.9, 3J ϭ J ϭ 9.0 Hz, 1 H, 6-H),
2
3
δB ϭ 1.65 (dtd, J ϭ Ϫ15.6, J ϭ 10.2 Hz, JH,F ϭ 5.2 Hz, 2 H, 6-
H), 1.0Ϫ0.8 (m, 2 H, 5-,7-Hendo]. 13C NMR (50.3 MHz): δ ϭ 25.1
(td, JC,F ϭ 6.9 Hz!, C-6), 26.3 (dd, JC,F ϭ 12 Hz, C-12), 30.3 (t),
34.4 (td, JC,F ϭ 27 Hz, C-11), 36.6 (t), 40.1 (dd, JC,F ϭ 1.6 Hz, C-
1), 98.5 (d, JC,F ϭ 194 Hz, C-10), 122.5 (dd, JC,F ϭ 4.9 Hz), 123.3
1.00Ϫ0.88 (m, 2 H, 5-,7-Hendo). 13C NMR (50.3 MHz): δ ϭ 23.7,
28.5 (C-12), 32 (C-4,-8), 37 (C-5,-7), 40.0 (C-1), 41.8 (C-11), 73.4
(C-10), 124.9 (d), 125.7 (d), 158.5 (s), 159.0 (s), signal of CN miss-
ing due to low intensity. 10-Chloro-12-cyanotricyclo[7.3.1.03,10]tri-
deca-2,9(13)-diene (9b): 1H NMR (400 MHz): δ ϭ 6.04 (dd, 3J ϭ
(dd, JC,F ϭ 5.4 Hz), 157.5 (d, JC,F ϭ 13 Hz), 157.9 (d, JC,F
ϭ
4
3
3
5.9, J ϭ 0.8 Hz, 1 H), 5.91 (d, J ϭ 5.8 Hz, 1 H), 3.83 (td, J ϭ
13 Hz), signal of CN missing due to low intensity. 19F NMR
3
3
3
3
5.9, J ϭ 2.8 Hz, 1 H, 1-H), 2.94 (ddd, J ϭ 10.4, J ϭ 4.6, J ϭ
2.8 Hz, 1 H, 12-H), 2.8Ϫ2.6 (m, 2 H, 4-,8-Hexo), 2.4Ϫ2.3 (m, 2 H,
(376.43 MHz): δ ϭ Ϫ12.3.
4-,8-Hendo), 2.30 [AB system: δA ϭ 2.37 (dd, 2J ϭ Ϫ12.5, 3J ϭ Reaction with 1f: Ratio 8f/9f ϭ 48:52. MS: m/z (%) ϭ 277 (1) [Mϩ·],
2
3
10.4 Hz, 1 H, 11-Hanti), δB ϭ 2.23 (dd, J ϭ Ϫ12.5, J ϭ 4.6 Hz,
224 (10), 198 (5) [M Ϫ Br], 169 (20), 145 (30), 115 (23), 84 (100).
1 H, 11-Hsyn)], 2.2Ϫ2.1 (m, 2 H, 5-,7-Hexo), 1.98 (dt, 2J ϭ Ϫ15.9, HRMS (C14H16BrN): calcd. 277.0466; found 277.0455. 10-Bromo-
3J ϭ 10.7 Hz, 1 H, 6-H), 1.56 (dt, J ϭ Ϫ15.9, J ϭ 9.0 Hz, 1 H, 11-cyanotricyclo[7.3.1.03,10]trideca-2,9(13)-diene (8f): 1H NMR
2
3
3
3
6-H), 1.00Ϫ 0.88 (m, 2 H, 5-,7-Hendo). 13C NMR (50.3 MHz): δ ϭ (400 MHz): δ ϭ 6.14 (d, J ϭ 5.9 Hz, 1 H), 6.11 (d, J ϭ 5.9 Hz,
23.7, 32 (C-4,-8), 36.9 (C-5,-7), 37.0 (C-12), 39.9 (C-1), 40 (C-11), 1 H), 3.64 (tt, 3J ϭ 5.9, J ϭ 3.0 Hz, 1 H, 1-H), 3.25 (dd, 3J ϭ 9.4,
3
Eur. J. Org. Chem. 2002, 614Ϫ629
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