Structural Effects on the Catalytic, Emulsifying, and Recycling Properties of Chiral Amphiphilic Dendritic Organocatalysts

Three series of chiral amphiphilic G1-G3 dendritic organocatalysts containing an optically active polar proline-derived core and one or two nonpolar hydrocarbon dendrons were prepared. These dendritic organocatalysts were employed in the asymmetric aldol and nitro-Michael additions in oil-in-water emulsions to reveal the effects of dendron size and branching on the catalytic properties. The incorporation, of larger hydrophobic dendrons has the advantages of promoting emulsion formation in water, improving the reaction enantioselectivity, decreasing catalyst loading (to 1 mol %), and facilitating catalyst recovery after the reactions. In general, the larger dendrons tended to lower catalyst reactivity due to their increasing steric blocking effect. However, some astonishing observations were found in some of the G1 and G2 dendritic organocatalysts, wherein an increase in the steric bulkiness and branching of the dendron resulted in better catalyst reactivity. It was also found that higher product yields and enantioselectivities were obtained in the aldol reactions when the aromatic aldehyde contains an electron-withdrawing substituent. The catalysts could be recycled and reused five times without significant drop in product yields and enantioselectivities. In addition, cross product contamination was not found when the recovered G3 catalyst was subsequently used in another reaction involving different substrates.