C-H, N-H Coupling of azoles takes place with several amines in the presence of a copper catalyst to undergo amination at the 2-position. The reaction of benzothiazole with N-methylaniline in the presence of sodium acetate and 20 mol % Cu(OAc)(2) in xylene under an oxygen atmosphere afforded the aminated product in 81% yield.

When several azole derivatives such as imidazole, thiazole, and oxazole are treated with a catalyst system of copper(II)/silver(I) under oxygen atmosphere, oxidative dimerization at the CH bond of the 2-position takes place to afford the corresponding bisazoles up to 86% yield.

C-H, N-H coupling of azole and thiophene derivatives takes place in the presence of a catalytic amount of Cu(OAc) 2 and an additive. The reaction of azoles smoothly occurs with several amines and amides catalyzed by 20 mol% of Cu(OAc) 2-2PPh 3 and 4 equiv. of NaOAc under O 2 or in the presence of Ag 2 CO 3 under N 2. The coupling reaction leads to a facile synthesis of a Nsubstituted analogue of 2,5-diarylthiazole, which shows photoluminescent properties with extended -conjugation. Spectroscopic characteristics of the obtained thiazole derivatives are discussed by measurements of UV-vis absorption and photoluminescent spectra. Under the reaction conditions using Ag 2 CO 3 as an additive and Cu(OAc) 2-2PPh 3 as a catalyst, thiophene derivatives also react with 2-pyrrolidone to undergo C-H, N-H amidation.

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General R 0010 Direct Amination of Azoles via Catalytic C-H, N-H Coupling. -Copper-catalyzed amination of heterocyclic C(sp 2 ) carbon with secondary amines proceeds smoothly under oxygen atmosphere to afford tertiary amines, e.g. (III), (V). -(MONGUCHI, D.; FUJIWARA, T.; FURUKAWA, H.; MORI*, A.; Org. Lett. 11