AlBr3-Promoted stereoselective anti-hydroarylation of the acetylene bond in 3-arylpropynenitriles by electron-rich arenes: synthesis of 3,3-diarylpropenenitriles

Reactions of 3-arylpropynenitriles (ArC≡CCN) with electron-rich arenes (Ar′H, benzene and its polymethylated derivatives) under the action of aluminum bromide (AlBr3, 6 equiv) at room temperature for 0.5–2 h result in the stereoselective formation of 3,3-diarylpropenenitriles (Ar(Ar′)C=CHCN) in yields of 20–64%, as products of mainly anti-hydroarylation of the acetylene bond. The obtained 3,3-diarylpropenenitriles in triflic acid CF3SO3H (TfOH) at room temperature for 1 h are cyclized into 3-arylindenones in yields of 55–70%.

Probing the Surface Acidity of Supported Aluminum Bromide Catalysts

Solid acid catalysis is an important class of reactions. The principal advantages of solid acid catalysts as compared to their corresponding fluid acids include minimal waste and ease of product separation. One type of these catalysts is based on aluminum bromide (Al2Br6), which is a stronger Lewis acid than Al2Cl6. In this report, Al2Br6 is grafted on commercial mesoporous silica (CMS), SBA-15 and silica gel to create a solid catalyst similar to the silica-supported Al2Cl6 superacid. These supported Al2Br6 catalysts were characterized by NH3-Temperature Programmed Desorption (TPD), pyridine Diffuse Reflectance for Infrared Fourier Transform Spectroscopy (DRIFTS) and Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Formation of acid sites was confirmed and quantified with NH3-TPD. Both Lewis and Brønsted sites were observed with DRIFTS using pyridine as a probe molecule. In addition, thermal stability of acid sites was also studied using DRIFTS. 27Al MAS NMR analysis showed tetrahedral, pentahedral and octahedral co-ordination of Al, confirming that Al2Br6 reacted with –OH groups on silica surface. Performance of these catalysts was evaluated using acid-catalyzed 1-butene isomerization. Conversion above 80% was observed at 200 °C, corresponding to thermodynamic equilibrium.

A Simple Aluminum Bromide-Promoted Diastereoselective Synthesis of Panduratin A Derivatives

A facile diastereoselective synthesis of panduratin A derivatives using commercially available aluminum(III) bromide is reported. The effect of substituents on the Diels–Alder reaction of various trans-chalcones with (E)-ocimene was investigated. A series of panduratin A derivatives were prepared in moderate to good yields.