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Synlett 2007(18): 2833-2836  
DOI: 10.1055/s-2007-990838
LETTER
© Georg Thieme Verlag Stuttgart · New York

[RuCl3(H2O)n]-Catalyzed Direct Arylations with Bromides as Electrophiles

Lutz Ackermann*, Andreas Althammer, Robert Born
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstr. 2, 37077 Göttingen, Germany
Fax: +49(551)396777; e-Mail: Lutz.Ackermann@chemie.uni-goettingen.de;
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Publication History

Received 12 August 2007
Publication Date:
12 October 2007 (online)

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Abstract

Catalytic amounts of [RuCl3(H2O)n] allow for direct ­arylations via C-H bond functionalization with aryl bromides, ­bearing a variety of important functional groups.

Key words

arene - aryl bromides - C-H bond functionalization - ­regioselectivity - ruthenium

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19

Representative Procedure - Synthesis of 3d (Table 1, Entry 3)
A suspension of 5 (12.6 mg, 0.05 mmol, 5.0 mol%), K2CO3 (415 mg, 3.00 mmol), 2-phenylpyridine (160 mg, 1.03 mmol), and 4-bromoacetophenone (438 mg, 2.20 mmol) in anhyd NMP (2.0 mL) was stirred for 22 h at 120 °C under N2. After the reaction mixture was cooled to ambient temperature, Et2O (50 mL) and H2O (40 mL) were added. The separated aqueous phase was extracted with Et2O (3 × 50 mL). The combined organic layers were washed with H2O (50 mL) and brine (50 mL), dried over Na2SO4, and concentrated in vacuo. The remaining residue was purified by column chromatography on silica gel (n-pentane-Et2O, 3:1 → 2:1 → 1:1 → 1:2 → 1:3) to yield 3d (361 mg, 90%, mp 200.5-201.5 °C) as a yellow solid. 1H NMR (300 MHz, CDCl3): δ = 8.30 (d, J = 5.0 Hz, 1 H), 7.75 (d, J = 8.1 Hz, 4 H), 7.56 (dd, J = 8.6, 6.4 Hz, 1 H), 7.50-7.45 (m, 2 H), 7.31 (dt, J = 7.7, 1.8 Hz, 1 H), 7.18 (d, J = 8.1 Hz, 4 H), 6.94 (ddd, J = 7.5, 4.8, 0.9 Hz, 1 H), 6.86 (d, J = 7.7 Hz, 1 H), 2.56 (s, 6 H). 13C NMR (75 MHz, CDCl3): δ = 197.7, 157.9, 148.7, 146.3, 140.9, 138.3, 135.3, 135.1, 129.8, 129.7, 128.5, 127.8, 126.6, 121.4, 26.5. IR (KBr): 3053, 2919, 1680, 1605, 1268, 958, 809 cm-1. MS (EI): m/z (%) = 391 (68) [M+], 390 (100), 348 (13). HRMS (EI): m/z calcd for C27H21NO2: 391.1572; found: 391.1550.