Useful DMAP Analogs

9-Azajulolidine (1) is a strong acylation catalyst, which displays remarkably enhanced catalytic activity toward the acylation of sterically hindered alcohols compared to 4-dimethylaminopyridine (DMAP) and other analogs.¹⁾
Because of its high electron-rich character, 1 is also useful as an effective auxiliary ligand for promoting post-Ullmann coupling reactions leading to the construction of C(aryl)-heteroatom bonds.²⁾ It can be applied to the synthesis of triarylamines, which are important hole-transporting materials in many organic optoelectronic devices.

Typical Procedure: C–N bond formation
CuI (9.5 mg, 0.05 mmol), base (2.0 mmol), aryl iodide (1.0 mmol) and aryl amine (1.2 mmol) are added to a two-neck flask equipped with a septum. The flask is evacuated and back-filled with argon. Then toluene (4 mL) and 9-azajulolidine (1.0 mL, 0.1 mmol, 0.1 M in toluene) are added by a syringe at room temperature. The reaction mixture is heated at 110 °C for 40 h. The reaction mixture is allowed to cool to room temperature, water (20 mL) is added, and the mixture is extracted with CH₂Cl₂ (15 mL × 3). The combined organic solution is dried over MgSO₄ and concentrated in vacuo to yield the crude product, which is purified by chromatography on silica gel.