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 followed 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 fluorescence 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 π-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 racemates, 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.