S. Bernhardt, M. Baumgarten, K. Müllen
131.8, 131.6, 131.4, 131.1, 130.2, 129.4 (all Carom.), 122.3, 121.8, gave the crude product, which was further purified by column
FULL PAPER
121.7, 121.5 (all C–Cϵ), 107.3, 107.2 (all CϵC–Si), 91.3, 91.2 (all
ϵC–Si), 19.0, 18.9, 18.9 (all CH3), 11.2 (CH) ppm. MALDI TOF
chromatography (petroleum ether/CH2Cl2) and precipitation from
methanol to afford 14b as a white solid. Yield: 70 mg (39 µmol),
mass: m/z (%) = 4552 (50), [M – 43, isopropyl]+, 4595 (100), [M]+, 66%. 1H NMR (700 MHz, CD2Cl2, 300 K): δ = 7.21 (s, 4 H,
4618 (20), [M + Na]+, 4633 (40) [M + K]+. C309H410OSi16 (4590):
calcd. C 80.86, H 9.00; found C 80.94, H 7.11.
H1st generation), 7.18–7.11 (m, 20 H, Harom.), 6.99 (s, 2 H, 4-HBp, 4Ј-
HBp), 6.93–6.92 (m, 12 H, Harom.), 6.86–6.83 (m, 22 H, Harom.),
6.78–6.75 (m, 16 H, Harom.), 6.68–6.67 (m, 4 H, Harom.), 6.63–6.61
(m, 8 H, Harom.), 6.53–6.52 (2s, 4 H, 2-HBp, 2Ј-HBp, 6-HBp, 6Ј-HBp),
11: Compound 10 (350 mg, 76.2 µmol) was dissolved in dry THF
(10 mL) and treated with TBAF (385 mg, 1.22 mmol) under argon
for 5 min. The reaction was quenched with H2O. Purification was
performed by precipitation from methanol/H2O to afford 11 as a
white solid. Yield: 125 mg (60 µmol), 78%. 1H NMR (500 MHz,
3
6.35–6.34 (d, JH,H = 8.8 Hz, 2 H, Harom), 3.80 (s, 3 H, CH3), 1.87
(s, 1 H, OH) ppm. 13C NMR (175 MHz, CD2Cl2, 300 K): δ =
158.6, 146.8, 142.1, 142.0, 141.2, 141.1, 141.0, 140.8, 140.5, 140.4,
139.7, 139.6, 138.1, 132.0, 131.9, 131.8, 131.4, 130.6, 130.3, 129.8,
128.2, 127.9, 127.8, 127.2, 126.9, 126.7, 126.0, 125.9, 125.7, 113.3,
81.3 (C–OH), 55.6 (CH3) ppm. FD mass (8 kV): m/z (%) = 1815.2
(100) [M]+, 1797.8 (30) [M – 17 = OH]+. C140H98O2 (1812.3): calcd.
C 92.78, H 5.45; found C 92.43, H 5.38.
CD2Cl2, 300 K): δ = 7.33–7.31 (m, 12 H, Harom.), 7.17 (s, 2 H, 4-
3
H
Bp, 4Ј-HBp), 7.11–7.03 (m, 28 H, Harom.), 6.98–6.96 (d, JH,H
=
3
8.2 Hz, 8 H, Harom.), 6.79–6.77 (d, JH,H = 8.2 Hz, 8 H, Harom.),
3
3
6.71–6.70 (d. JH,H = 8.2 Hz, 8 H, Harom.), 6.67–6.65 (d, JH,H
=
8.2 Hz, 8 H, Harom.), 3.13–2.99 (4s, 16 H, ϵCH) ppm. 13C NMR
(175 MHz, CD2Cl2, 300 K): δ = 195.3 (C=O), 141.9, 141.3, 141.3,
140.8, 140.6, 140.4, 140.4, 140.3, 139.3, 139.2, 137.3, 135.3, 132.0,
131.7, 131.6, 131.5, 131.4, 131.3, 131.2, 130.2, 129.2 (all Carom.),
120.9 120.3, 120.1 (all C–Cϵ), 83.5, 83.6, (all CϵCH) 78.1, 78.0,
77.7, 77.7 (all ϵCH) ppm. MALDI TOF mass: m/z (%) = 2090
(100) [M]+, 4182 (10) [2 M]+ (C165H90O calcd. 2089).
14c: Compound 8 (96 mg, 56.3 µmol) was dissolved in dry THF
(5 mL) under argon. A solution of n-butyllithium (2 mL, 3.2 mmol,
1.6 ) in hexane was added through a septum and the mixture
heated at 70 °C for 16 h. Afterwards H2O (5 mL) was added, the
mixture extracted with CH2Cl2/H2O and the organic solvent re-
moved under reduced pressure. The crude product was purified by
column-chromatographie (petroleum ether/CH2Cl2) and precipi-
tation from methanol to afford 14c as a white solid. Yield: 70 mg
12: A mixture of 11 (60 mg, 28.7 µmol) and 7 (530 mg, 1.38 mmol)
was dissolved in o-xylene (4 mL) and refluxed at 170 °C for 3 days
under argon. The solvent was removed under reduced pressure and
the crude product purified by column chromatography (petroleum
ether/CH2Cl2). Precipitation from methanol afforded 12 as a white
solid. Yield: 190 mg (24.4 µmol), 85%. 1H NMR (500 MHz,
CD2Cl2, 300 K): δ = 7.43–7.39 (m, 20 H, H1st+2nd generation), 7.26 (s,
1
(39 µmol), 70%. H NMR (500 MHz, CD2Cl2, 300 K): δ = 7.24 (s,
4 H, H1st generation), 7.17–7.12 (m, 20 H, Harom.), 6.96–6.69 (m, 63
H, Harom.), 6.61 (s, 4 H, 2-HBp, 2Ј-HBp, 6-HBp, 6Ј-HBp), 1.28–1.24
3
(m, 4 H, α-CH2, β-CH2), 1.15–1.06 (sept, 2 H, JH,H = 7.4 Hz, γ-
3
CH2), 0.81 (t, JH,H = 7.2 Hz, 3 H, CH3) ppm. 13C NMR
(125 MHz, CD2Cl2, 300 K): δ = 146.5 (CBp-1, CBp-1Ј), 142.0, 141.9,
141.1, 141.0, 140.9, 140.8, 140.4, 139.6, 139.5, 131.9, 131.8, 131.7,
131.3, 130.3, 129.9, 127.8, 127.2, 127.1, 126.8, 126.6, 125.9, 125.6,
77.5 (C–OH), 40.9 (α-CH2), 25.4 (β-CH2), 23.3 (γ-CH2), 14.2
(CH3) ppm. FD mass (8 kV): m/z (%) = 1761.5 (100) [M]+.
C137H100O (1762.3): calcd. C 93.37, H 5.72; found C 93.04, H 5.61.
4 H, Harom.), 7.13 (m, 370 H, Harom.), 6.54–6.34 (s, 16 H, Harom.
)
ppm. 13C NMR (175 MHz, CD2Cl2, 300 K): δ = 196.4 (C=O),
142.2, 142.2, 142.1, 142.1, 142.0, 142.0, 141.2, 141.1, 141.0, 141.0,
140.8, 140.6, 140.6, 140.5, 140.4, 139.7, 139.6, 139.6, 139.4, 139.3,
131.9, 131.5, 131.5, 131.4, 130.3, 130.3, 130.2, 130.2, 129.7, 129.6,
127.9, 127.8, 127.8, 127.2, 127.1, 127.1, 126.9, 126.9, 126.5, 126.5,
126.0, 125.9, 125.6, 125.5 ppm. MALDI TOF mass: m/z = 7792
(100) [M]+, 7819 (40) [M + Na]+, 7898 (45) [M + Ag]+. C613H410
(7792): calcd. C 94.49, H 5.30; found C 94.46, H 5.33.
O
Acknowledgments
14a: Compound 8 (110 mg, 64.5 µmol) was dissolved in dry THF
(5 mL) under argon. A solution of phenyllithium (2 mL, 3.8 mmol,
1.8–2.1 ) in cyclohexane/ether (70:30) was added through a sep-
tum and the mixture heated at 70 °C for 16 h. Then H2O (5 mL)
was added, the mixture extracted with CH2Cl2/H2O and the or-
ganic solvent removed under reduced pressure. The crude product
was purified by column chromatography (petroleum ether/CH2Cl2)
and precipitation from methanol to afford 14a as a white solid.
Yield: 80 mg (45 µmol), 70%. 1H NMR (500 MHz, CD2Cl2,
300 K): δ = 7.21 (s, 4 H, H1st generation), 7.16–7.11 (m, 20 H, Harom.),
Financial support by the Deutsche Forschungsgemeinschaft (SFB
625) is gratefully acknowledged. We thank C. Beer for synthetic
support.
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J. M. J. Fréchet, J. Polym. Sci., Part A: Polym. Chem. 2003, 41,
3713–3725; c) G. R. Newkome, C. N. Moorefield, F. Vögtle,
Dendrimers and Dendrons: Concepts, Syntheses, Application;
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J. M. J. Fréchet, D. Tomalia, Dendrimers and Other Dendritic
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Chem. Rev. 1999, 99, 1665–1688.
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[3] a) C. M. Cardona, T. Wilkes, W. Ong, A. E. Kaifer, T. D.
McCarley, S. Pandey, G. A. Baker, M. N. Kane, S. N. Baker,
F. V. Bright, J. Phys. Chem. B 2002, 106, 8649–8656; b) J. M.
Riley, S. Alkan, A. D. Chen, M. Shapiro, W. A. Khan, W. R.
Murphy, J. E. Hanson, Macromolecules 2001, 34, 1797–1809;
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6.99–6.62 (m, 65 H, Harom.), 6.53 (s, 4 H, 2-HBp, 2Ј-HBp, 6-HBp
,
3
6ЈHBp), 6.47–6.46 (d, JH,H = 8.5 Hz, 2 H, 4-HBp, 4Ј-HBp), 1.89 (s,
1 H, OH) ppm. 13C NMR (125 MHz, CD2Cl2, 300 K): δ = 146.6,
145.6, 142.1, 141.1, 141.0, 140.8, 140.5, 140.3, 139.8, 139.6, 131.9,
131.8, 131.8, 131.3, 130.6, 130.3, 128.2, 128.1, 128.0, 127.9, 127.3,
127.2, 126.9, 126.7, 125.9, 125.7, 81.6 (C–OH) ppm. FD mass
(8 kV): m/z (%) = 1783.7 (100), [M]+, 892.3 (85) [M]2+. C139H96O
(1782.3): calcd. C 93.67, H 5.43; found C 93.67, H 5.48.
14b: Compound 8 (100 mg, 58.7 µmol) was placed in a Schlenck
tube under argon. (4-Methoxyphenyl)magnesium bromide (3 mL,
1.5 mmol, 0.5 in THF) was added and the reaction mixture re-
fluxed at 70 °C for 24 h. After cooling, H2O (5 mL) was added and
the solution stirred for another 30 min. Extraction with CH2Cl2/
H2O and concentration of the organic layer under reduced pressure
2528
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Eur. J. Org. Chem. 2006, 2523–2529