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Synlett 2009(19): 3192-3194  
DOI: 10.1055/s-0029-1218307
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Cobalt-Catalyzed Arylation or Benzylation of 2-Chloro-4,6-dimethoxy-1,3,5-triazine

Jeanne Marie Bégouina, Stéphanie Claudela, Corinne Gosmini*b
a Institut de Chimie et des Matériaux Paris Est, ICMPE, CNRS-Université de Paris, 12 Val de Marne, UMR7182, 2-8 rue Henri Dunant, 94320 Thiais, France
b Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, 91128 Palaiseau Cedex, France
Fax: +33(1)69334440; e-Mail: corinne.gosmini@polytechnique.edu;
Further Information

Publication History

Received 11 September 2009
Publication Date:
23 October 2009 (online)

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Abstract

A variety of functionalized aryl bromides or benzyl chlorides were coupled with 2-chloro-4,6-dimethoxy-1,3,5-trazine in good yields by a one-step procedure via cobalt catalysis.

Key words

cobalt - catalysis - cross-coupling - arylation - azo compounds

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16

Representative Experimental Procedure for the Synthesis of 2-Aryl-4,6-dimethoxy-1,3,5-triazines and 2-Benzyl-4,6-dimethoxy-1,3,5-triazines from Aryl Bromides or Benzyl Chlorides; Zinc Insertion and Cross-Coupling: To a solution of CoBr2 (10 mol%, 0.75 mmol, 165 mg) and zinc powder (19 mmol, 1.2 g) in MeCN (6 mL) were successively added at r.t. allyl chloride (2.25 mmol, 190 µL) and trifluoroacetic acid (100 µL), causing an immediate rise in temperature and color change to dark grey. After stirring the resulting mixture for 3 min, aryl bromide or benzyl chloride (7.5 mmol) and 2-chloro-4,6-dimethoxy-1,3,5-triazine (10 mmol, 1.7 g) were added. The medium was then stirred at r.t. until aryl or benzyl halide was consumed. The amount of the corresponding coupling product was measured by GC (by addition of iodine) using an internal reference (dodecane, 100 µL). The reaction mixture was poured into a sat. aq solution of NH4Cl and extracted with CH2Cl2. The organic layer was washed with a sat. aq solution of NaCl and dried over MgSO4. Evaporation of the solvent and purification by column chromatography on silica gel (pentane-Et2O) afforded the coupling product characterized by NMR (¹H, ¹³C, ¹9F), mass spectrometry and elementary analysis for new products.