Synthesis and Chiroptical Properties of Helical Polyallenes Bearing Chiral Amide Pendants
Synthesis and Chiroptical Properties of Helical Polyallenes Bearing Chiral Amide Pendants
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DOI：
10.1021/ma5019022
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发表时间：
2014-10
期刊：
影响因子：
5.5
通讯作者：
Yuanyuan Zhu;Ting-Ting Yin-Ting;Xue-liang Li;Ming‐Hsin Su;Ya-Xin Xue;Zhi-peng Yu;Na Liu;Jun Yin
中科院分区：
文献类型：
--
作者：
Yuanyuan Zhu;Ting-Ting Yin-Ting;Xue-liang Li;Ming‐Hsin Su;Ya-Xin Xue;Zhi-peng Yu;Na Liu;Jun Yin
设计并合成了两种带有手性酰胺侧链的丙二烯衍生物，l-和d-N-(1-(辛氨基)-1-氧代丙烷-2-基)-4-(丙-1,2-二烯-1-基氧基)苯甲酰胺(l-1和d-1)。 l-1和d-1与烯丙基镍配合物作为催化剂进行活性聚合，得到具有受控分子量和窄分子量分布的聚-l-1m和聚-d-1m。根据圆二色性（CD）光谱和比旋光度以及计算机模拟，发现这些聚合物在非质子溶剂中具有稳定的螺旋构象和优选的旋向性。结果表明，聚合物的螺旋构象通过重复单元的伸长而稳定，直到聚合度达到80。温度对CHCl3中poly-l-1100的圆二色光谱的轻微影响表明螺旋构象至少在0-55°C范围内相当稳定。尽管 Poly-l-1100 在不同的非质子溶剂中显示出相似的 CD 光谱，但显着降低...
Two allene derivatives, l- and d-N-(1-(octylamino)-1-oxopropan-2-yl)-4-(propa-1,2-dien-1-yloxy)benzamide (l-1 and d-1), bearing chiral amide pendants were designed and synthesized. Living polymerizations of l-1 and d-1 with allylnickel complex as a catalyst afforded poly-l-1m and poly-d-1m with controlled molecular weights and narrow molecular weight distributions. These polymers were found to possess a stable helical conformation with a preferred handedness in aprotic solvents on the basis of their circular dichroism (CD) spectra and specific rotation as well as computer simulation. The helical conformation of the polymers was revealed to be stabilized by elongation of the repeating unit until the degree of the polymerization reaches 80. The slightly influence of temperature on the CD spectra of poly-l-1100 in CHCl3 indicated the helical conformation was quite stable at least in the range of 0–55 °C. Although poly-l-1100 showed similar CD spectra in different aprotic solvents, remarkable decrease was obs...