Aryl iodides benzotriazole

The arylation of nitrogen-containing heterocycles, such as benzotriazole, with aryl iodides can be done only in anhydrous media under rather harsh conditions (DMSO, DBU, 120°C, Pd2(DBA)3-CHCl3) No reaction occurred in the presence of the water-soluble TPPMS ligand. However, the arylation can be accomplished with diaryliodonium salts in neat water under phosphine-less conditions and in the absence of copper salt promoter [88]. Both products of substitution are formed, as the anion of benzotriazole is an ambident nucleophile ... 

The reaction of benzotriazoles with aryl halides catalyzed by a mixture of Pd(dppe)Cl2 (DPPE = bis-(diphenylphosphino)ethane) or Pd(dppf)Cl2, copper(I)iodide or copper(II)carboxylates, and a phase-transfer catalyst has been shown to proceed in good yield in DMF solvent.104 Both copper and palladium were required for these reactions to occur at the N-l position in high yields. Similar results for the coupling of amines with aryliodonium salts in aqueous solvent were observed.105... 

Benzotriazole was found to be an efficient ligand for the Cu(I) iodide-catalyzed N-arylation of imidazoles with aryl and heteroaryl halides <07TL4207>. The first enantioselective conjugate addition reaction of I //-benzotriazole with a variety of enones catalyzed by a cinchona alkaloid thiourea affords Michael adducts in good yields with moderate to good enantioselectivities has been reported <07S2576>. 

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