J. Sakamoto, A. D. Schlüter
FULL PAPER
The mixture was stirred at 60 °C for 1 d. After cooling to room
temperature and evaporation under reduced pressure, the residue
was purified by GPC (Bio-RAD SX1) to afford 844 mg of 18 (45%)
22.5, 20.9, 19.90, 19.83, 18.53, 18.51, 18.38, 13.9, 11.6, 11.12,
11.11 ppm. HRMS (MALDI, 3-HPA): m/z calcd. for [M + H]+
1623.888; found 1623.884.
1
and 625 mg of 19a (25%). Compound 18: H NMR: δ = 8.93 (d,
Compound 22b: Acetic acid (45 µL, 0.79 mmol) and, dropwise, a
1.0 THF solution of TBAF (0.75 mL) were added to a solution
of 22a (600 mg, 0.369 mmol) in dry THF (26 mL). The mixture
was stirred at room temperature for 16 h, diluted with chloroform
(300 mL), washed successively with sat. aq. NaHCO3/brine (1:1)
and with brine, and dried with MgSO4. After evaporation under
reduced pressure, the residue was purified by GPC (Bio-RAD SX1)
4J = 2.4 Hz, 1 H, pyridinyl-H), 8.86 (d, 4J = 2.4 Hz, 1 H, pyridinyl-
3
4
H), 8.52 (d, J = 8.3 Hz, 2 H, pyridinyl-H), 8.04 (dd, J = 2.4 Hz,
4
3
3J = 8.3 Hz, 1 H, pyridinyl-H), 7.98 (dd, J = 2.4 Hz, J = 8.3 Hz,
1 H, pyridinyl-H), 7.86 (m, 1 H, phenyl-H), 7.71 (m, 2 H, phenyl-
H), 7.59 (m, 1 H, phenyl-H), 7.56–7.52 (m, 3 H, phenyl-H), 7.46
(m, 1 H, phenyl-H), 7.36 (m, 1 H, phenyl-H), 7.34 (s, 1 H, Cm2),
6.93 (s, 1 H, Cm2), 6.10 (d, 1 H, Cm2), 4.56 [s, 2 H, ben-
zyl(OC6H13)-H], 4.49 [s, 2 H, benzyl(OC6H13)-H], 4.15 [s, 2 H, ben-
zyl(Cm2)-H], 3.50 (m, 4 H, α-CH2), 3.06 (q, 2 H, Cm2), 2.40 (s, 3
H, Cm2), 2.35 (d, 3 H, Cm2), 1.63 (m, 4 H, β-CH2), 1.42–1.23 (m,
12 H, δ-, γ-, ε-CH2), 1.11 (s, 21 H, TIPS), 1.05 (t, 3 H, Cm2), 0.87
(t, 6 H, CH3) ppm. 13C NMR: δ = 161.3, 154.6, 154.3, 153.2, 152.6,
152.1, 147.3, 141.9, 140.2, 139.5, 138.9, 137.7, 136.0, 135.7, 135.4,
135.3, 135.0, 134.9, 133.9, 131.5, 130.8, 130.3, 129.5, 129.2, 126.5,
126.1, 125.3, 123.92, 123.87, 123.3, 121.2, 121.1, 115.0, 112.7,
109.2, 105.9, 95.0, 91.6, 89.4, 89.1, 72.1, 71.6, 71.0, 70.9, 55.9, 46.6,
31.61, 31.60, 29.65, 29.61, 25.82, 25.80, 22.56, 22.55, 18.6, 18.5,
14.0, 11.6, 11.2 ppm. HRMS (MALDI, 3-HPA): m/z calcd. for [M
+ H]+ 1172.520; found 1172.521. Compound 19a: 1H NMR: δ =
1
to afford 364 mg of 22b (75%). H NMR: δ = 8.87 (s, 2 H, pyridi-
nyl-H), 8.47 (d, 3J = 8.3 Hz, 2 H, pyridinyl-H), 8.22 (s, 1 H,
Cm343), 7.98 (d, 3J = 8.3 Hz, 2 H, pyridinyl-H), 7.66 (m, 2 H,
phenyl-H), 7.60 (m, 1 H, phenyl-H), 7.58–7.47 (m, 9 H, phenyl-H),
7.45 (m, 1 H, phenyl-H), 7.38 (m, 1 H, phenyl-H), 7.29 (s, 1 H,
Cm2), 6.87 (s, 1 H, Cm2), 6.78 (s, 1 H, Cm343), 6.04 (d, 1 H, Cm2),
5.24 [s, 2 H, benzyl(Cm343)-H], 4.51 [s, 4 H, benzyl(OC6H13)-H],
4.10 [s, 2 H, benzyl(Cm2)-H], 3.48 (t, 4 H, α-CH2), 3.21 (m, 4 H,
Cm343), 3.09 (s, 1 H, ethynyl-H), 3.08 (s, 1 H, ethynyl-H), 3.01 (q,
2 H, Cm2), 2.74 (t, 2 H, Cm343), 2.62 (t, 2 H, Cm343), 2.35 (s, 3
H, Cm2), 2.29 (s, 3 H, Cm2), 1.84 (m, 4 H, Cm343), 1.60 (m, 4 H,
β-CH2), 1.41–1.19 (m, 12 H, δ-, γ-, ε-CH2), 1.01 (t, 3 H, Cm2),
0.83 (t, 6 H, CH3) ppm. 13C NMR: δ = 163.8, 161.1, 158.2, 154.68,
154.63, 153.3, 153.0, 152.4, 152.1, 149.2, 148.6, 147.4, 140.04,
140.03, 139.0, 137.75, 137.71, 137.0, 135.25, 135.23, 135.0, 134.4,
133.8, 131.3, 131.2, 131.1, 130.12, 130.08, 129.3, 129.0, 126.9,
126.5, 126.0, 123.6, 123.5, 123.3, 122.6, 122.5, 120.8, 119.1, 114.8,
112.5, 108.9, 107.2, 105.9, 105.3, 89.8, 89.6, 88.7, 88.6, 82.5, 82.3,
78.2, 78.0, 72.0, 70.78, 70.77, 65.0, 55.7, 50.0, 49.6, 46.5, 31.5, 29.5,
27.1, 25.7, 22.4, 20.8, 19.84, 19.77, 18.5, 18.3, 13.9, 11.5 ppm.
HRMS (MALDI, 3-HPA): m/z calcd. for [M + H]+ 1311.621;
found 1311.623.
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8.93 (d, J = 2.2 Hz, 2 H, pyridinyl-H), 8.54 (d, J = 8.3 Hz, 2 H,
pyridinyl-H), 8.04 (dd, 4J = 2.2 Hz, 3J = 8.3 Hz, 2 H, pyridinyl-H),
7.71 (m, 2 H, phenyl-H), 7.59 (m, 2 H, phenyl-H), 7.53 (m, 4 H,
phenyl-H), 7.46 (m, 2 H, phenyl-H), 7.35 (m, 2 H, phenyl-H), 7.33
(s, 2 H, Cm2), 6.92 (s, 2 H, Cm2), 6.09 (m, 2 H, Cm2), 4.55 [s, 4
H, benzyl(OC6H13)-H], 4.14 [s, 4 H, benzyl(Cm2)-H], 3.51 (t, 4 H,
α-CH2), 3.05 (q, 4 H, Cm2), 2.40 (s, 6 H, Cm2), 2.33 (d, 6 H, Cm2),
1.63 (m, 4 H, β-CH2), 1.43–1.20 (m, 12 H, δ-, γ-, ε-CH2), 1.10 (s,
42 H, TIPS), 1.04 (t, 6 H, Cm2), 0.86 (t, 6 H, CH3) ppm. 13C NMR:
δ = 161.2, 154.5, 153.2, 152.5, 152.1, 147.4, 140.2, 138.9, 137.8,
135.6, 135.3, 133.8, 131.5, 130.7, 130.2, 129.4, 129.1, 126.5, 126.0,
123.9, 123.8, 123.3, 121.1, 114.9, 112.7, 109.2, 105.9, 91.6, 89.4,
89.1, 72.1, 70.9, 55.9, 46.6, 31.6, 29.6, 25.8, 22.5, 18.55, 18.53, 18.4,
14.0, 11.6, 11.2 ppm. HRMS (MALDI, 3-HPA): m/z calcd. for [M
+ H]+ 1155.898; found 1155.894.
Compound 19b: Acetic acid (20 µL, 0.35 mmol) and, dropwise, a
1.0 THF solution of TBAF (0.33 mL) were added to a solution
of 19a (249 mg, 0.160 mmol) in dry THF (12 mL). The mixture
was stirred at room temperature for 20 h. After evaporation under
reduced pressure, the residue was purified by silica gel column
chromatography (hexane/ethyl acetate, 3:2) to afford 150 mg of 19b
Compound 22a: [Pd(PPh3)4] (20 mg, 0.017 mmol) was added to a
carefully degassed mixture of 18 (364 mg, 0.310 mmol) and 7
(180 mg, 0.310 mmol) in dry THF/triethylamine (1:1, 20 mL). The
mixture was stirred at 60 °C for 38 h. After cooling to room tem-
perature and evaporation under reduced pressure, the residue was
purified by GPC (Bio-RAD SX1) to afford 472 mg of 22a (94%).
1
4
(76%). H NMR: δ = 8.90 (d, J = 2.3 Hz, 2 H, pyridinyl-H), 8.50
(d, 3J = 8.4 Hz, 2 H, pyridinyl-H), 8.01 (dd, 4J = 2.3 Hz, 3J =
8.4 Hz, 2 H, pyridinyl-H), 7.68 (m, 2 H, phenyl-H), 7.57 (m, 2 H,
phenyl-H), 7.51 (m, 4 H, phenyl-H), 7.46 (m, 2 H, phenyl-H), 7.39
(m, 2 H, phenyl-H), 7.31 (s, 2 H, Cm2), 6.90 (s, 2 H, Cm2), 6.07
(m, 2 H, Cm2), 4.53 [s, 4 H, benzyl(OC6H13)-H], 4.11 [s, 4 H, ben-
zyl(Cm2)-H], 3.50 (t, 4 H, α-CH2), 3.07 (s, 2 H, ethynyl-H), 3.02
(q, 4 H, Cm2), 2.37 (s, 6 H, Cm2), 2.31 (d, 6 H, Cm2), 1.62 (m, 4
H, β-CH2), 1.42–1.22 (m, 12 H, δ-, γ-, ε-CH2), 1.02 (t, 6 H, Cm2),
0.84 (t, 6 H, CH3) ppm. 13C NMR: δ = 161.3, 154.5, 153.1, 152.5,
152.1, 147.4, 140.1, 139.1, 137.8, 135.4, 135.2, 133.9, 131.4, 131.3,
130.2, 129.4, 129.1, 126.5, 126.1, 123.7, 123.4, 122.5, 121.0, 114.9,
112.6, 109.0, 89.6, 88.8, 82.5, 78.0, 72.0, 70.8, 55.8, 46.5, 31.5, 29.6,
25.7, 22.5, 18.5, 18.4, 13.9, 11.6 ppm. HRMS (MALDI, 3-HPA):
m/z calcd. for [M + H]+ 1243.631; found 1243.629.
3
1H NMR: δ = 8.91 (s, 2 H, pyridinyl-H), 8.52 (d, J = 8.3 Hz, 2 H,
pyridinyl-H), 8.25 (s, 1 H, Cm343), 8.03 (d, 3J = 8.3 Hz, 2 H, pyrid-
inyl-H), 7.70 (m, 2 H, phenyl-H), 7.61 (m, 2 H, phenyl-H), 7.58 (m,
2 H, phenyl-H), 7.52 (m, 3 H, phenyl-H), 7.50 (m, 1 H, phenyl-H),
7.45 (m, 1 H, phenyl-H), 7.34 (m, 1 H, phenyl-H), 7.32 (s, 1 H,
Cm2), 6.90 (s, 1 H, Cm2), 6.80 (s, 1 H, Cm343), 6.06 (d, 1 H, Cm2),
5.26 [s, 2 H, benzyl(Cm343)-H], 4.54 [s, 4 H, benzyl(OC6H13)-H],
4.13 [s, 2 H, benzyl(Cm2)-H], 3.50 (t, 4 H, α-CH2), 3.23 (m, 4 H,
Cm343), 3.04 (q, 2 H, Cm2), 2.76 (t, 2 H, Cm343), 2.64 (t, 2 H,
Cm343), 2.38 (s, 3 H, Cm2), 2.32 (s, 3 H, Cm2), 1.87 (m, 4 H,
Cm343), 1.62 (m, 4 H, β-CH2), 1.42–1.21 (m, 12 H, δ-, γ-, ε-CH2), Compounds 20a and 21a: [Pd(PPh3)4] (14 mg, 0.012 mmol) was
1.10 (s, 21 H, TIPS), 1.09 (s, 21 H, TIPS), 1.03 (t, 3 H, Cm2), 0.85
added to a carefully degassed mixture of 7 (346 mg, 0.596 mmol)
and 8b (470 mg, 0.596 mmol) in dry THF/triethylamine (1:2,
(t, 6 H, CH3) ppm. 13C NMR: δ = 163.8, 161.2, 158.3, 154.3, 153.3,
153.1, 152.5, 152.1, 149.2, 148.6, 147.3, 140.1, 138.9, 137.66, 30 mL). The mixture was stirred at 60 °C for 43 h. After cooling
137.62, 136.9, 135.53, 135.51, 135.3 134.6, 133.8, 131.4, 131.0, to room temperature and evaporation under reduced pressure, the
130.7, 130.2, 129.4, 129.0, 126.9, 126.5, 126.0, 124.0, 123.82, residue was purified by GPC (Bio-RAD SX1) to afford 290 mg of
1
123.75, 123.73, 123.4, 123.2, 121.1, 119.1, 114.8, 112.6, 109.0, 20a (39%) and 112 mg of 21a (11%). Compound 20a: H NMR: δ
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4
107.3, 106.0, 105.9, 105.6, 105.4, 91.7, 91.5, 89.6, 89.4, 89.0, 88.8,
= 8.88 (d, J = 2.3 Hz, 1 H, pyridinyl-H), 8.81 (d, J = 2.3 Hz, 1
3
72.0, 70.82, 70.80, 65.2, 55.7, 50.1, 49.7, 46.6, 31.5, 29.6, 27.2, 25.7, H, pyridinyl-H), 8.46 (d, J = 8.3 Hz, 2 H, pyridinyl-H), 8.24 (s, 1
2708
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 2700–2712