Wang Fan, Wang Weiqi, Wang Yuqing, Zheng Wei, Zheng Ting, Zhang Lili, Okamoto Yoshio, Shen Jun
Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China.
Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China.
Carbohydr Polym. 2023 Jul 1;311:120769. doi: 10.1016/j.carbpol.2023.120769. Epub 2023 Mar 6.
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.
通过氨基甲酰化反应，然后进行铃木-宫浦偶联反应，成功合成了三种带有大体积对位取代苯并噻吩基或苯并呋喃基侧链的新型直链淀粉和纤维素苯基氨基甲酸酯衍生物，作为手性荧光传感器。在本研究中，这些大体积衍生物对总共八种手性猝灭剂表现出良好的对映选择性荧光传感性能。特别是，直链淀粉苯并呋喃基苯基氨基甲酸酯（Amy-2）对重要的手性药物中间体3-氨基-3-苯基丙醇（Q5）实现了高对映体荧光差异率（ef = 164.35）。这表明，通过在围绕螺旋主链的苯基氨基甲酸酯部分上排列大体积的π共轭苯并噻吩基或苯并呋喃基侧链，有效地构建了有利的手性环境，这对于高效手性荧光传感至关重要。作为高效液相色谱的手性固定相，直链淀粉和纤维素的大体积苯并噻吩基苯基氨基甲酸酯对包括金属三（乙酰丙酮）配合物、手性药物、具有轴手性的分析物和手性芳香胺在内的十三种外消旋体也表现出良好的拆分能力，即使在流行的Chiralpak AD和Chiralcel OD上也难以有效分离。激发依赖的手性荧光传感可能遵循与基于基态分子动态碰撞的色谱对映体拆分不同的机制。还通过圆二色光谱和偏光显微镜研究了大体积衍生物的结构。
