Liu Lijia, Zhang Geng, Aoki Toshiki, Wang Yudan, Kaneko Takashi, Teraguchi Masahiro, Zhang Chunhong, Dong Hongxing
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.
Graduate School of Science and Technology, Niigata University, Nishi-ku, Niigata, 950-2181, Japan.
ACS Macro Lett. 2016 Dec 20;5(12):1381-1385. doi: 10.1021/acsmacrolett.6b00809. Epub 2016 Nov 29.
By using a living one-handed helical poly(chiral substituted phenylacetylene) as a polymer initiator (poly()), helix-sense-selective polymerization () of an achiral phenylacetylene having two hydroxy groups successfully afforded a diblock copoly(phenylacetylene) (copoly(/)) consisting of a dynamic one-handed helical block and a static one-handed helical block. The formation of the diblock structure was confirmed by consumption of the chiral initiator, appearance of characteristic CD indicating the one-handed helical block, and occurrence of the selective photocylic aromatization reaction in the block. Therefore, has been achieved by using the chiral alkenyl groups in the initiator as a chiral source for the first time. In addition, since the was achieved in spite of the long distance between the chiral initiation site and the propagating site, chiral teleinduction through the rigid and static one-handed helical -cisoidal block based on domino effects was confirmed.
通过使用一种活性单手螺旋聚（手性取代苯乙炔）作为聚合物引发剂（聚（）），具有两个羟基的非手性苯乙炔的螺旋方向选择性聚合（）成功地得到了一种由动态单手螺旋嵌段和静态单手螺旋嵌段组成的二嵌段共聚（苯乙炔）（共聚（/））。通过手性引发剂的消耗、表明单手螺旋嵌段的特征圆二色性的出现以及嵌段中选择性光环化芳构化反应的发生，证实了二嵌段结构的形成。因此，首次通过使用引发剂中的手性烯基作为手性源实现了。此外，尽管手性引发位点与增长位点之间距离很长，但仍实现了，这证实了基于多米诺效应通过刚性和静态单手螺旋 - 顺式块的手性远程诱导。
