Regioselectively substituted cellulose mixed esters synthesized by two-steps route to understand chiral recognition mechanism and fabricate high-performance chiral stationary phases

Abstract

It is challenging to design and fabricate new and high-performance cellulose-based chiral stationary phases (CSPs), due to the indistinct chiral recognition mechanism and the inherent difficulty to control the structure of cellulose derivatives. Herein, taking advantage of the high regioselective benzoylation of cellulose in 1-allyl-3-methylimidazolium chloride, a series of regioselectively substituted cellulose mixed esters, cellulose 6-benzoate-2,3-phenylcarbamate, are directly obtained by a facile two-steps route without protecting and deprotecting process. The resultant cellulose mixed esters exhibit high chiral recognition capability. In particular, when the benzoate group has an electron-donating substituent on phenyl ring, such as 4-tert-butyl group, the corresponding regioselectively substituted cellulose mixed esters have much better enantioseparation capability than cellulose tri(3,5-dimethylphenylcarbamate), which is commercially available as Chiralcel OD column, one of the most powerful CSPs. More importantly, via adjusting the chemical structure of cellulose derivatives and adding a post-treatment process to optimize their chiral recognition properties, the chiral recognition mechanism is clearly revealed. The synergy of the hydrophobic helical conformation, weak hydrogen-bond donating ability and appropriate distribution of substituents of cellulose derivatives is essential to fabricate high-performance CSPs.