Synlett 2017; 28(18): 2407-2410
DOI: 10.1055/s-0036-1588417
cluster
© Georg Thieme Verlag Stuttgart · New York

Nickel-Catalyzed N-Arylation Using N-Trimethylsilyl-carbazole

Yasunori Minami*a, Takeshi Komiyamab, Kenta Shimizub, Shu-ichi Unob, Tamejiro Hiyama*a, Osamu Gotoc, Hideyuki Ikehirad
  • aResearch and Development Initiative, Chuo University, Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan   Email: yminami@kc.chuo-u.ac.jp   Email: thiyama@kc.chuo-u.ac.jp
  • bFaculty of Science and Engineering, Chuo University, Kasuga, Bunkyo-ku, Tokyo 112-8551 Japan
  • cSumitomo Chemical, 3-1-98 Kasugadenaka, Konohana-ku, Osaka, 554-8558, Japan
  • dSumika Technical Information Service, 4-6-17 Koraibashi,Chuo-ku, Osaka, 541-0043, Japan
Supported by: Grants-in-Aid for Young Scientists (B) 25870747
Supported by: Japan Science and Technology Agency ACT-C
Further Information

Publication History

Received: 06 March 2017

Accepted after revision: 11 April 2017

Publication Date:
08 May 2017 (eFirst)

Published as part of the Cluster Silicon in Synthesis and Catalysis

Abstract

Nickel-catalyzed N-arylation reaction of N-trimethylsilyl-carbazole using aryl bromides is found to proceed in the presence of sodium acetate, giving N-aryl-carbazoles in high yields. Under these conditions, N-trimethylsilyl-carbazole could react with aryl bromides selectively even in the presence of other N-trimethylsilyl-amines or N-H-amines. This arylation reaction was applied to the polymerization to provide a polycarbazole.

Supporting Information

 
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  • 10 General Experimental Procedure for the Synthesis of N-Aryl-carbazoles A mixture of Ni(cod)2 (0.050 mmol), SIPr·HCl (0.050 mmol), KOt-Bu (0.050 mmol), and CPME was stirred at 100 °C for 30 min. To this was added NaOAc (0.85 mmol), aryl bromide 1 (0.50 mmol), and N-TMS-carbazole 2 (0.65 mmol). The reaction mixture was quenched with H2O. The aqueous layer was extracted with Et2O and washed with brine. The combined organic layers were dried over anhydrous MgSO4. After concentration in vacuo, the residue was purified by flash chromatography on silica gel or preparative TLC to afford N-aryl-carbazoles 3. N-(4-Methoxyphenyl)-3,6-dichloro-9H-carbazole (3j) was obtained according to the general experimental procedure. Pale yellow solid; yield 140 mg (78%). 1H NMR (400 MHz, CDCl3): δ = 3.90 (s, 3 H), 7.08 (d, J = 9.2 Hz, 2 H), 7.19 (d, J = 8.8 Hz, 2 H), 7.32–7.35 (m, 4 H), 8.00 (d, J = 2.0 Hz, 2 H). 13C NMR (126 MHz, CDCl3): δ = 55.7, 111.1, 115.4, 120.2, 123.3, 125.6, 126.8, 128.5, 129.5, 140.2, 159.4. MS (EI, 70 eV): m/z (%) = 341 (100) [M+], 326 (33), 306 (3), 262 (16), 228 (14), 171 (4).
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  • 12 The Supporting Information can be used for detailed procedures and the characterization data of other products.