L. Minuti et al. / Tetrahedron Letters 46 (2005) 5735–5737
5737
1
2
2
43.2 (C-3); MS m/e (rel. int.) 104 (38), 141 (15), 185 (61),
89.34; H, 6.53; N, 4.34. 5: white crystals (95% yield); mp
+
00 (100), 304 (M , 53); UV–vis (CHCl
1
3
) [kmax nm (loge)]:
84 (2.76); Anal. Calcd for C H Si: C, 82.83; H, 7.94.
148–149 °C (MeOH); H NMR d 2.80 (ddd, 1H, J = 13.0,
10.4, 5.5 Hz, H-2), 2.90–3.10 (m, 5H, H-1, H -9, H -10),
2
1
24
s
s
Found: C, 82.81; H, 7.95.(b) Bondarenko, L.; Dix, I.;
Hinrichs, H.; Hopf, H. Synthesis 2004, 2751–2759.
. (a) Ernst, L.; Wittkowski, L. Eur. J. Org. Chem. 1999,
3.20 (m, 1H, H-1), 3.80 (s, 3H, OMe), 3.58 (ddd, 1H,
J = 13.0, 10.1, 2.7 Hz, H-2), 6.45–6.55 (m, 3H, H-12, H-13,
H-16), 6.47 (d, 1H, J = 7.9 Hz, H-8), 6.52 (dd, 1H, J = 7.9,
1.9 Hz, H-7), 6.53 (d, 1H, J = 1.8 Hz, H-5), 6.86 (m, 2H,
7
8
1653–1663; (b) Morisaki, Y.; Fujimura, F.; Chujo, Y.
Organometallics 2003, 22, 3553–3557.
0 0
H-5 , H-7 ), 6.95 (dd, 1H, J = 7.7, 1.8 Hz, H-15), 7.42 (m,
0 0
13
. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron
Lett. 1975, 16, 4467–4470; (b) Takahashi, K.; Kuroyama,
Y.; Sonogashira, K.; Hagihara, N. Synthesis 1980, 627–
2H, H-4 , H-8 ); C NMR d 34.6 (C-2), 34.8 (C-1), 35.4,
35.7 (C-9, C-10), 55.6 (OMe), 85.7 (C-1 ), 93.1 (C-2 ),
0
0
0
0
0
114.3 (C-5 , C-7 ), 116.3 (C-3 ), 125.5 (C-4), 130.2 (C-15),
132.6, 132.9, 133.1, 133.5, 134.1 (C-7, C-8, C-12, C-13, C-
6
30; (c) Sonogashira, K. In Metal Catalyzed Cross-
0
0
Coupling Reactions; Diederich, F., Stang, P. J., Eds.;
Wiley-VCH: Weinheim, 1998, Chapter 5.
. Diarylacetylenes 12 and 13 were prepared according to a
16, C-4 , C-8 ), 137.1 (C-5), 139.6 (C-6), 139.8, 139.9 (C-
0
11, C-14), 142.5 (C-3), 159.8 (C-6 ); MS m/e (rel. int.) 189
+
(17), 219 (15), 234 (100), 338 (M , 38); UV–vis (CHCl
9
3
)
1
0
previouslydescribed procedure bySonogashira coupling
between p-diiodobenzene and the commerciallyavailable
[kmax nm(loge)]: 335 (4.92); Anal. Calcd for C25H22O: C,
88.72; H, 6.55. Found: C, 89.35; H, 6.58. 6: orange crystals
8
b,11
1
p-ethynylaniline (10) and p-ethynylanisole (11).
noteworthythat in the case of 13 the reaction yield was
It is
(95% yield); mp 80–81 °C (MeOH); H NMR d 2.89 (ddd,
1H, J = 13.3, 10.4, 5.3 Hz, H-2), 2.95–3.16 (m, 5H, H-1,
improved from 65% to 90% byemplo yi ng Pd(PPh
and Et NH.
3
)
2
Cl
2
s s
H -9, H -10), 3.26 (m, 1H, H-1), 3.66 (ddd, 1H, J = 13.3,
10.2, 2.6 Hz, H-2), 3.85 (br s, 2H, NH ), 6.48 (d, 1H,
2
2
1
1
1
0. Mongin, O.; Gossauer, A. Tetrahedron 1997, 53, 6835–
846.
1. Elangovan, A.; Yang, S.-W.; Lin, J.-M.; Kao, K.-M.; Ho,
T.-I. Org. Biomol. Chem. 2004, 2, 1597–1602.
2. General procedure for the Sonogashira reaction of 4-
ethynyl[2.2]paracyclophane (3) with aryliodides 8, 9 and
diaryliodides 12 and 13. The following discussion of the
J = 7.8 Hz, H-8), 6.51 (dd, 1H, J = 7.8, 2.0 Hz, H-7), 6.48–
6.55 (m, 3H, H-12, H-13, H-16), 6.58 (d, 1H, J = 2.0 Hz,
6
0 0
H-5), 6.64 (m, 2H, H-13 , H-15 ), 7.01 (dd, 1H, J = 7.8,
0
0
1.9 Hz, H-15), 7.35 (m, 2H, H-12 , H-16 ), 7.50–7.53 (m,
0 0 0 0
13
4H, H-4 , H-5 , H-7 , H-8 ); C NMR d 34.6 (C-1), 34.8
(C-2), 35.4, 35.7 (C-9, C-10), 87.5 (C-9 ), 91.6 (C-1 ), 92.4
0
0
0
0
0
0
0
(C-10 ), 93.0 (C-2 ), 112.7 (C-11 ), 115.0 (C-13 , C-15 ),
123.2, 123.9 (C-3 , C-6 ), 125.0 (C-4), 130.4 (C-15), 131.5
0 0
3
–8 reaction is a typical procedure used for all coupling
reactions. Dry THF (6 ml), 4-ethynyl[2.2]paracyclophane
3) (0.189 g, 0.81 mmol), triphenylphosphine (0.021 g,
.08 mmol), CuI (0.008 g, 0.04 mmol), 4-iodoaniline (8)
0.118 g, 0.54 mmol) and the palladium catalyst (0.028 g,
.04 mmol) were placed in a flask and degassed with Ar.
0
0
0
0
(C-4 , C-5 , C-7 , C-8 ), 132.7, 132.9, 133.0, 133.5 (C-12,
0
0
(
0
(
0
C-13, C-16), 133.1 (C-7), 133.3 (C-12 , C-16 ), 134.1 (C-8),
137.2 (C-5), 139.6 (C-11), 139.7 (C-6), 140.0 (C-14), 142.7
0
(C-3), 147.1 (C-14 ); UV–vis (CHCl ) [k
nm (loge)]: 347
(2.99); Anal. Calcd for C32H25N: C, 90.74; H, 5.95; N,
3
max
The mixture was heated at 75 °C for 20 h. Then, the
solvent was removed under reduced pressure and the
residue was chromatographed on silica gel. Elution with
petroleum ether/dichloromethane 1:2 afforded 0.145 g
3.31. Found: C, 90.92; H, 5.93; N, 3.27. 7: pale yellow
crystals (90% yield); mp 179–180 °C (MeOH); H NMR d
2.90 (ddd, 1H, J = 13.2, 10.4, 5.4 Hz, H-2), 2.92–3.15 (m,
1
5H, H-1, H
J = 13.2, 10.3, 2.8 Hz, H-2), 3.84 (s, 3H, OCH
s
-9, H
s
-10), 3.25 (m, 1H, H-1), 3.66 (ddd, 1H,
), 6.49 (d,
(
(
83% yield) of 4 as pale orange crystals; mp 173–174 °C
3
1
MeOH); H NMR d 2.85 (m, 1H, H-2), 2.9–3.15 (m, 5H,
1H, J = 7.8 Hz, H-8), 6.48–6.56 (m, 3H, H-12, H-13, H-
16), 6.53 (dd, 1H, J = 7.8, 1.9 Hz, H-7), 6.58 (d, 1H,
H-1, H
3
6
s
-9, H
.81 (br s, 2H, –NH
.54 (m, 4H, H-7, H-12, H-13, H-16), 6.52 (d, 1H,
s
-10), 3.25 (m, 1H, H-1), 3.65 (m, 1H, H-2),
0 0
J = 1.9 Hz, H-5), 6.89 (m, 2H, H-13 , H-15 ), 7.02 (dd, 1H,
2
), 6.42 (d, 1H, J = 7.9 Hz, H-8), 6.44–
0
0
J = 7.8, 1.8 Hz, H-15), 7.49 (m, 2H, H-12 , H-16 ), 7.51–
0 0 0 0
0
0
13
7.55 (m, 4H, H-4 , H-5 , H-7 , H-8 ); C NMR d 34.6 (C-
J = 1.7 Hz, H-5), 6.68 (m, 2H, H-5 , H-7 ), 7.05 (dd, 1H,
0
0
13
J = 7.7, 1.9 Hz, H-15), 7.40 (m, 2H, H-4 , H-8 ); C NMR
1), 34.8 (C-2), 35.4, 35.7 (C-9, C-10), 55.5 (OCH
0
3
), 88.2
0
0
0
0
0
0
d 34.5 (C-1), 34.8 (C-2), 35.4, 35.7 (C-9, C-10), 87.9 (C-1 ),
(C-9 ), 91.5 (C-1 ), 91.7 (C-2 ), 92.9 (C-10 ), 114.3 (C-13 ,
0
0
0
0
0
0
0
9
3.8 (C-2 ), 113.6 (C-3 ), 115.1 (C-5 , C-7 ), 125.8 (C-4),
C-15 ), 115.5 (C-11 ), 123.5 (C-6 ), 124.9 (C-4, C-3 ), 130.4
0
0
0
0
1
C-16, C-4 , C-8 ), 134.0 (C-8), 137.0 (C-5), 139.6 (C-11),
30.2 (C-15), 132.4, 132.9 (C-7, C-12), 133.0, 133.5 (C-13,
0
(C-15), 131.6, 131.7 (C-4 , C-5 , C-7 , C-8 ), 132.7, 132.9
0
0
0
(C-12, C-16), 133.2 (C-7), 133.3 (C-12 , C-16 ), 133.5 (C-
13), 134.1 (C-8), 137.2 (C-5), 139.6 (C-11), 139.7 (C-6),
140.0 (C-14), 142.7 (C-3), 160.1 (C-14 ); UV–vis (CHCl )
3
0
1
39.8 (C-6, C-14), 142.3 (C-3), 146.8 (C-6 ); MS m/e (rel.
+
0
int.) 103 (5), 147 (4), 165 (4), 189 (8), 219 (100), 323 (M ,
6); UV–vis (CHCl ) [kmax nm (loge)]: 276 (3.49); Anal.
Calcd for C24 21N: C, 89.12; H, 6.54; N, 4.33. Found: C,
3
3
[kmax nm (loge)]: 336 (4.65); Anal. Calcd for C33H26O: C,
90.38; H, 5.98. Found: C, 90.82; H,5.94.
H