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(2-Bromo-2Ј,6Ј-dimethoxy-5-methylbiphenyl-3-yl)trimethylsilane
(2p-a): Butyllithium (2.00 mmol) in hexane (1.25 mL) was added
dropwise to a solution of 1,3-dimethoxybenzene (0.28 g,
2.00 mmol) in anhydrous THF (5.00 mL) under Ar at 0 °C. The
mixture was stirred at 25 °C for 5 h and was then cooled to –78 °C.
A solution of the 1,2-dibromobenzene 1p (0.77 g, 2.40 mmol) in
anhydrous THF was added dropwise. The mixture was stirred at
–78 °C for 3 h and then warmed to 25 °C overnight. Water (60 mL)
was added and the mixture was extracted with Et2O (3ϫ40 mL).
The combined organic layers were dried with Na2SO4 and evapo-
rated under reduced pressure. Purification of the crude product by
column chromatography (cyclohexane/CH2Cl2, 75:25) afforded the
[4]
[5]
[6]
1
biaryl 2p-a (0.47 g, 62%) as a colorless solid; m.p. 117–118 °C. H
NMR (300 MHz, CDCl3): δ = 0.42 [s, 9 H, Si(CH3)3], 2.33 (s, 3 H,
Ar-CH3), 3.74 (s, 6 H, 2 OCH3), 6.65 (d, J = 8.3 Hz, 2 H, Ar-H),
7.04 (d, J = 1.9 Hz, 1 H, Ar-H), 7.23 (d, J = 1.9 Hz, 1 H, Ar-H),
7.32 (t, J = 8.3 Hz, 1 H, Ar-H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 0.0 (3 CH3), 21.1 (CH3), 56.2 (2 CH3), 104.3 (2 CH), 120.2 (C),
129.3 (CH), 130.0 (C), 133.9 (CH), 135.7 (C), 136.2 (CH), 136.3
(C), 141.1 (C), 157.9 (2 C) ppm. C18H23BrO2Si (379.36): C 56.99,
H 6.11; found C 56.81, H 6.27.
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(4Ј-Bromo-2ЈЈ,6ЈЈ-dimethoxy-1,1Ј:3Ј,1ЈЈ-terphenyl-5Ј-yl)trimethyl-
silane (2q-a): Butyllithium (2.00 mmol) in hexane (1.25 mL) was
added dropwise to a solution of 1,3-dimethoxybenzene (0.28 g,
2.00 mmol) in anhydrous THF (5.00 mL) under Ar at 0 °C. The
mixture was stirred at 25 °C for 5 h and was then cooled to –78 °C.
A solution of the 1,2-dibromobenzene 1q (0.92 g, 2.40 mmol) in
anhydrous THF was added dropwise. The mixture was stirred at
–78 °C for 3 h and then warmed to 25 °C overnight. Water (60 mL)
was added and the mixture was extracted with Et2O (3ϫ40 mL).
The combined organic layers were dried with Na2SO4 and evapo-
rated under reduced pressure. Purification of the crude product by
column chromatography (cyclohexane/CH2Cl2, 75:25) followed by
crystallization from EtOH afforded the biaryl 2q-a (0.41 g, 47%)
[9]
[10]
[11]
[12]
1
as a colorless solid; m.p. 138–140 °C. H NMR (CDCl3): δ = 0.47
[s, 9 H, Si(CH3)3], 3.75 (s, 6 H, 2 OCH3), 6.67 (d, J = 8.4 Hz, 2 H,
Ar-H), 7.30–7.44 (m, 5 H, Ar-H), 7.59–7.63 (m, 3 H, Ar-H) ppm.
13C NMR (CDCl3): δ = 0.1 (3 CH3), 56.2 (2 CH3), 104.2 (2 CH),
119.9 (C), 127.3 (2 CH), 127.4 (CH), 128.8 (2 CH), 129.5 (CH),
132.0 (CH), 132.5 (C), 133.8 (CH), 136.9 (C), 139.1 (C), 140.8 (C),
141.9 (C), 157.9 (2 C) ppm. C23H25BrO2Si (441.43): C 62.58, H
5.71; found C 62.47, H 5.63.
[13]
Supporting Information (see also the footnote on the first page of
1
this article): H and 13C NMR spectra.
[14]
[15]
Acknowledgments
We are grateful to the Centre National de la Recherche Scientifique
(CNRS), the Ministère de l’Education Nationale et de la Recher-
che, and the Agence Nationale pour la Recherche (ANR program
07-BLAN-0292-01, MetChirPhos) for financial support and a post-
doctoral grant to V. D. The authors thank Patrick Wehrung for his
valuable support in HRMS analysis.
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obtained free of charge from The Cambridge Crystallographic
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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