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FULL PAPER
The resin was transferred to a syringe filter and washed with alternating
rinses of CH2Cl2 and MeOH (43 mL). The resin was then treated with
K2CO3 in THF/MeOH 4:1 for 12 h. The filtrate was removed, concentrat-
ed, dissolved in ether, and filtered through a plug of silica gel to yield the
cyclotrimerized product. Yields ranged from 52–87% and products were
obtained in quantities of 6.4–2.2 mg.
1.55 (m, 2H), 1.40–1.32 (m, 2H), 0.93 ppm (t, 3J
ACHTREUNG
LCMS: m/z: 257.1 ppm [M+Na]+, tR =6.73 min.
Compound 43: 1H NMR (300 MHz, CDCl3): d=7.55 (d, 3J
ACHTREUNG
6.9 Hz, 2H), 7.43–7.23 (m, 6H), 3.82 (s, 4H), 2.91 (s, 2H), 2.90 (s, 2H),
2.34 ppm (s, 2H); 13C NMR (75 MHz, CDCl3): d=142.4, 141.6, 140.9,
140.1, 128.9, 127.3, 127.2, 125.9, 125.5, 124.0, 69.9, 49.5, 38.8, 38.6 ppm;
HRMS (FAB): m/z calcd for C17H19O2: 255.1385; found: 255.1381
[M+H]+; LCMS: m/z: 277.0 [M+Na]+, tR =6.16 min.
Cyclotrimerization of 26 by using [Cp*ClRu(cod)] as the catalyst: Deriv-
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atized resin 26 (50 mg, 0.05 mmol) was placed in a flame-dried vial with
dichloroethane (2 mL). The soluble alkyne (0.50 mmol, 10 equiv) was
added and the solution was degassed with three freeze-pump-thaw cycles.
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Compound 44: H NMR (300 MHz, CD3OD): d=7.14–7.09 (m, 3H), 4.53
(s, 2H), 3.78 (s, 4H), 2.76 ppm (s, 4H); LCMS: m/z: 231.0 [M+Na]+, tR =
[Cp*ClRu(cod)] catalyst (2 mg, 0.01 mmol, 0.1 equiv) was added and the
N
3.89 min.
reaction was shaken at room temperature for 24 h. The resin was trans-
ferred to a syringe filter and washed with alternating rinses of CH2Cl2
and MeOH (43 mL). The resin was then treated with K2CO3 in THF/
MeOH 4:1 for 12 h. The filtrate was removed and concentrated to yield
the cyclotrimerized product. Yields ranged from 69–95% and products
were obtained in quantities of 8.1–3.9 mg.
Compound 28:[38] 1H NMR (300 MHz, CD3OD): d=10.46 (s, 2H), 7.28–
7.24 (m, 4H), 4.50 ppm (s, 4H); LCMS: m/z: 119.1 [M+H]+, tR =
4.04 min.
Compound 45: 1H NMR (300 MHz, CDCl3): d=7.37–7.15 (m, 8H), 4.56
(s, 2H), 4.52 (s, 2H), 3.75 (s, 4H), 2.83 (s, 4H), 2.23 ppm (s, 2H); LCMS:
m/z: 321.1 [M+Na]+, tR =6.07 min.
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Compound 46: H NMR (300 MHz, CD3OD): d=7.25–7.20 (m, 3H), 4.04
(s, 2H), 3.55 (s, 4H), 2.81 ppm (s, 4H); LCMS: m/z: 230.0 [M+Na]+, tR =
1.97 min.
Compound 47: 1H NMR (300 MHz, CDCl3): d=7.12–6.94 (m, 3H), 3.76
(s, 4H), 2.83 (s, 2H), 2.81 (s, 2H), 2.74 (t, 3J
ACHTREUNG
2.30 (m, 2H), 2.29 (s, 2H), 1.97 ppm (t, 3J
ACHTREUNG
Compound 29: 1H NMR (300 MHz, CDCl3): d=10.40 (s, 2H), 7.12 (d,
(75 MHz, CDCl3): d=142.5, 140.1, 138.3, 127.0, 125.4, 125.3, 119.9, 69.7,
49.3, 38.6, 38.4, 34.5, 27.3, 16.6 ppm; HRMS (EI): m/z: calcd for
C15H20NO2 [M+H]+: 246.1494; found: 246.1488; LCMS: m/z: 268.0
[M+Na]+, tR =5.12 min.
Compound 48: 1H NMR (300 MHz, CDCl3): d=7.35–7.15 (m, 3H), 3.77
(s, 4H), 2.85 (s, 4H), 2.43 (s, 2H), 0.25 ppm (s, 9H); LCMS: m/z: 273.0
[M+Na]+, tR =6.77 min.
3J
C
ACHTREUNG
ACHTREUNG
1.35 (m, 2H), 0.93 ppm (t, 3J
[M+H]+, tR =5.93 min.
Compound 30: 1H NMR (300 MHz, CDCl3): d=10.49 (s, 2H), 7.56–7.33
(m, 8H), 4.73 ppm (s, 4H); 13C NMR (75 MHz, CDCl3): d=142.6, 140.2,
134.8, 132.9, 129.1, 128.3, 128.0, 127.4, 123.4, 121.7, 50.9, 50.7 ppm;
HRMS (FAB): m/z: calcd for C14H14N: 196.1126; found: 196.1114
[M+H]+; LCMS: m/z: 196.1 [M+H]+, tR =5.75 min.
Compound 49: 1H NMR (300 MHz, CDCl3): d=7.10–6.94 (m, 3H), 3.77
(s, 4H), 3.55 (t, 3J
N
N
7.5 Hz, 2H), 2.32–2.10 (brs, 2H), 1.84–1.75 ppm (m, 4H); LCMS: m/z:
Compound 31: 1H NMR (300 MHz, CD3OD): d=7.39 (d, 3J
(H,H)=
U
291.0 [M+Na]+, tR =6.36 min.
7.6 Hz, 2H), 7.38 (s, 1H), 4.63 (s, 4H), 3.09 ppm (s, 2H); LCMS: m/z:
Compound 50: 1H NMR (300 MHz, CDCl3): d=8.58 (s, 1H), 8.25–7.93
150.1 [M+H]+, tR =1.97 min.
(m, 2H), 3.76 (s, 4H), 3.59 (s, 3H), 3.25 ppm (d, 3J
LCMS: m/z: 259.0 [M+Na]+, tR =5.57 min.
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Compound 32: 1H NMR (300 MHz, CDCl3): d=10.42 (s, 2H), 7.35–7.22
(m, 8H), 4.64 (s, 4H), 4.55 (s, 2H), 4.53 ppm (s, 2H); LCMS: m/z: 240.1
[M+H]+, tR =5.81 min.
Compound 51: 1H NMR (300 MHz, CDCl3): d=6.99 (s, 2H), 3.78 (s,
4H), 2.81 (s, 4H), 2.62 (q, 3J
C
Compound 33: 1H NMR (300 MHz, CD3OD): d=7.52 (d, 3J
A
3
(t, J
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8.1 Hz, 2H), 7.50 (s, 1H), 4.67 (s, 4H), 4.17 ppm (s, 2H); LCMS: m/z:
Compound 52: 1H NMR (300 MHz, CDCl3): d=7.20 (s, 2H), 4.74 (s,
4H), 3.74 (s, 4H), 3.93 (s, 6H), 2.82 (s, 4H), 2.34–2.22 ppm (brs, 2H);
LCMS: m/z: 289.1 [M+Na]+, tR =4.72 min.
149.1 [M+H]+, tR =1.34 min.
Compound 34: 1H NMR (300 MHz, CDCl3): d=10.52 (s, 2H), 7.23–7.12
(m, 3H), 4.67 (s, 4H), 2.35 (t, 3J
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ACHTREUNG
Compound 54: 1H NMR (300 MHz, CDCl3): d=7.28–7.18 (m, 3H), 5.19
7.2 Hz, 2H), 2.00 ppm (quin, 3J
ACHTREUNG
(s, 2H), 5.12 (s, 2H), 4.67 ppm (d, 3J
151.0 [M+H]+, tR =5.37 min.
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CDCl3): d=141.2, 134.7, 132.3, 129.5, 123.4, 123.1, 119.3, 50.7, 50.6, 34.4,
27.1, 16.8 ppm; HRMS (FAB): m/z: calcd for C12H15N2: 187.1235; found:
187.1231 [M+H]+; LCMS: m/z: 187.1 [M+H]+, tR =4.41 min.
Compound 55: 55a/55b 1:3; 1H NMR (300 MHz, CDCl3): d=7.11 (s,
0.5H), 7.06 (s, 0.75H), 7.00 (s, 0.75H), 5.24 (s, 1H), 5.15 (s, 1.5H), 5.09
Compound 35: 1H NMR (300 MHz, CDCl3): d=10.44 (s, 2H), 7.47 (d,
(1.5H), 4.87 (s, 0.5H), 4.64 (s, 1.5H), 2.71 (t, 3J
(H,H)=7.8 Hz, 0.5H),
H
3J
(H,H)=7.5 Hz, 1H), 7.43 (s, 1H), 7.29 (s, 1H), 4.68 (s, 4H), 0.28 ppm
G
2.63 (t, 3J(H,H)=7.8 Hz, 1.5H), 1.43–1.30 (m, 4H), 0.92 ppm (t, 3J=
N
(s, 9H); LCMS: m/z: 192.0 [M+H]+, tR =6.37 min.
7.2 Hz, 3H); LCMS: m/z: 207.1 [M+H]+, tR =8.25 min.
Compound 36: 1H NMR (300 MHz, CDCl3): d=10.41 (s, 2H), 7.25–7.09
Compound 56: 56a/56b 3:1; 1H NMR (300 MHz, CDCl3): d=7.57 (d,
(m, 3H), 4.63 (s, 4H), 3.55 (t, 3J
U
G
3J
(H,H)=6.9 Hz, 0.5H, 7.44–7.35 (m, 5H), 7.22 (s, 1.5H), 5.32 (s, 1.5H),
R
3
5.22 (s, 1H), 5.17 (s, 1.5H), 4.73 (d, J
A
6.03 min.
3J(H,H)=5.4 Hz, 1.5H); 13C NMR (75 MHz, CDCl3): d=141.6, 141.1,
AHCTREUNG
Compound 37: 1H NMR (300 MHz, CDCl3): d=10.43 (s, 2H), 8.03 (m,
2H), 7.95 (s, 1H), 3.92 (s, 3H), 3.48 ppm (s, 4H); LCMS: m/z: 178.1
[M+H]+, tR =5.34 min.
140.8, 136.7, 134.8, 129.0, 127.7, 127.4, 125.2, 119.2, 73.7, 72.7, 63.9 ppm;
HRMS (FAB): m/z calcd for C15H15NO2 [M+H]+: 227.1072; found:
227.1069; LCMS: m/z: 227.0 [M+H]+, tR =7.64 min.
Compound 57: 57a/57b 1:1; 1H NMR (300 MHz, CDCl3): d=7.67–7.44
(m, 1H), 7.17 (s, 0.5H), 7.14 (s, 0.5H), 5.22–5.10 (m, 4H), 4.77–4.66 ppm
(m, 4H); LCMS: m/z: 203.0 [M+Na]+, tR =4.50 min.
Compound 38: 1H NMR (300 MHz, CDCl3): d=10.31 (s, 2H), 7.06 (s,
2H), 4.61 (s, 4H), 2.64 (q, 3J
U
G
Compound 39: 1H NMR (300 MHz, CDCl3): d=10.34 (s, 2H), 7.33 (s,
2H), 4.64 (s, 4H), 4.49 (s, 4H), 3.40 ppm (s, 6H); LCMS: m/z: 208.1
[M+H]+, tR =4.20 min.
Compound 41:[39] 1H NMR (300 MHz, CDCl3): d=7.18–7.13 (m, 4H),
3.78 (s, 4H), 2.86 (s, 4H), 2.39 ppm (s, 2H); LCMS: m/z: 179.0 [M+Na]+,
tR =5.01 min.
Compound 58: 58a/58b 1:1; 1H NMR (300 MHz, CDCl3): d=7.37–7.16
(m, 7H), 5.24 (s, 1H), 5.17 (s, 1H), 5.12 (d, 3J
(H,H)=4.5 Hz, 2H), 4.67
T
(s, 2H), 4.60–4.56 ppm (m, 4H); LCMS: m/z: 293.0 [M+Na]+, tR =
7.83 min.
Compound 59: 59a/59b 1:1; 1H NMR (300 MHz, CDCl3): d=7.24–7.09
(m, 3H), 5.23–5.02 (m, 4H), 4.65 (d, 3J
ACHTREUNG
Compound 42: 1H NMR (300 MHz, CDCl3): d=7.08–6.95 (m, 3H), 3.77
3J
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ACHTREUNG
(s, 4H), 2.81 (s, 4H), 2.57 (t, 3J
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Chem. Eur. J. 2006, 12, 5563 – 5568
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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