Synthesis of amylose and cellulose derivatives bearing bulky pendants for high-efficient chiral fluorescent sensing

Three novel amylose and cellulose phenylcarbamate derivatives bearing bulky para-substituted benzothienyl or benzofuranyl pendants were successfully synthesized as chiral fluorescent sensors through carbamoylation fol-lowed by Suzuki-Miyaura coupling reactions. The bulky derivatives showed good enantioselective fluorescent sensing properties toward a total of eight chiral quenchers in this study. Especially, a high enantiomeric fluo-rescence difference ratio (ef = 164.35) was achieved on amylose benzofuranylphenylcarbamates (Amy-2) to the 3-amino-3-phenylpropan-1-ol (Q5), an important chiral drug intermediate. It indicated that a favorable chiral environment was effectively constructed by arrangement of bulky pi-conjugated benzothienyl or benzofuranyl pendants on the phenylcarbamate moieties surrounding the helical backbone, which is crucial for high-efficient chiral fluorescent sensing. As chiral stationary phases for high-performance liquid chromatography, the bulky benzothienylphenylcarbamates of amylose and cellulose also showed good resolution powers to thirteen race -mates, including metal tris(acetylacetonate) complexes, chiral drugs, analytes with axial chirality and chiral aromatic amines, which were difficult to be efficiently separated even on the popular Chiralpak AD and Chiralcel OD. The excitation-dependent chiral fluorescent sensing probably followed different mechanisms from that for chromatographic enantioseparation relying on the dynamic collision of molecules in the ground state. The structure of the bulky derivatives was also investigated by CD spectra and POM microscopy.

Automated summary

Three novel amylose and cellulose phenylcarbamate derivatives were synthesized as chiral fluorescent sensors, showing good enantioselective properties. These derivatives demonstrated high efficiency in chiral fluorescent sensing for important chiral drug intermediates and also displayed good resolution powers as chiral stationary phases in high-performance liquid chromatography. The excitation-dependent chiral fluorescent sensing mechanism was found to be different from chromatographic enantioseparation.