Chiral imidazole metalloenzyme models: Synthesis and enantioselective hydrolysis for α-amino acid esters

Chiral imidazole hydrolytic metalloenzyme models with characteristics of chiral centers directly link to imidazole N-atoms and varieties in both alkyl chain length and number of alkyl chains, have been synthesised and investigated for enantioselective hydrolysis of Boc-α-amino acid esters. The result indicates that both hydrolysis rates and enantioselectivities are increased with increases in the alkyl chain length and the number of the alkyl chains in the lipophilic chiral imidazole-type surfactants in many cases. The lipophilic chiral imidazole 4d ((S)-1-hexadecoxy-2-(1-imidazolyl)-propane), which has one long alkyl chain, shows higher hydrolysis rate and enantioselectivity (kD = 132.5 × 10−5, kD/kL = 5.38), 5d ((S)-1,5-dihexadecoxy-2-(1-imidazolyl)-pentane), which has two long alkyl chains, shows the highest hydrolysis rate and enantioselectivity (kD = 201.5 × 10−5, kD/kL = 11.72). Additionally, the effects of the metals, the additives, the solvents and the substrates on the hydrolysis rates and enantioselectivities are examined.

Graphical abstractChiral imidazole hydrolytic metalloenzyme models have been synthesised and investigated for enantioselective hydrolysis of Boc-α-amino acid esters, and the result indicates that both hydrolysis rates and enantioselectivities are increased with increases in the alkyl chain length and the number of the alkyl chains in the lipophilic chiral imidazole-type surfactants in many cases. Figure optionsDownload full-size imageDownload as PowerPoint slide