Enantioselective Living Coordinative Chain Transfer Polymerization: Production of Optically Active End-Group-Functionalized (+)- or (−)-Poly(methylene-1,3-cyclopentane) via a Homochiral C 1 -Symmetric Caproamidinate Hafnium Initiator
Enantioselective Living Coordinative Chain Transfer Polymerization: Production of Optically Active End-Group-Functionalized (+)- or (−)-Poly(methylene-1,3-cyclopentane) via a Homochiral C 1 -Symmetric Caproamidinate Hafnium Initiator
复制标题
对映选择性活性配位链转移聚合：通过同手性 C 1 -对称己脒铪引发剂生产光学活性端基官能化 ( )- 或 (-)-聚(亚甲基-1,3-环戊烷)
DOI：
10.1021/acscatal.0c02104
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发表时间：
2020
期刊：
影响因子：
12.9
通讯作者：
Sita, Lawrence R.
中科院分区：
文献类型：
--
作者：
Wallace, Mark A.;Zavalij, Peter Y.;Sita, Lawrence R.
纯手性、构型稳定的C1-对称二甲基、五甲基、N-（S）-或N-（R）-1-苯基乙基-己脒合铪预引发剂（SC，SHf）-1和（RC，RHf）-1可分别与硼酸盐共引发剂[PhNHMe 2][B（C6 F5）4]（B）和过量当量的ZnEt 2组合用于1的对映选择性活性配位链转移聚合（LCCTP），5-己二烯，以提供具有可调分子量和非常窄的多分散性的（+）-和（−）-聚（亚甲基-1，3-环戊烷）（PMCP）。使用过量的I2淬灭LCCTP，得到相应的（+）-和（−）-碘封端的PMCP产物。这种对映选择性LCCTP方法用于建立对用于材料科学和技术发现的光学活性液晶端基官能化xPMCP构建块的容易获得的、实用的和可扩展的量的访问。
The homochiral, configurationally stable,C1-symmetric dimethyl, pentamethylcyclopentadienyl,N-(S)- orN-(R)-1-phenylethyl-caproamidinate hafnium preinitiators(SC,SHf)-1and(RC,RHf)-1, respectively, can be used in combination with the borate coinitiator [PhNHMe2][B(C6F5)4] (B) and excess equivalents of ZnEt2for the enantioselective living coordinative chain transfer polymerization (LCCTP) of 1,5-hexadiene to provide (+)- and (−)-poly(methylene-1,3-cyclopentane) (PMCP) of tunable molecular weight and very narrow polydispersity. Use of excess I2to quench LCCTP provides the corresponding (+)- and (−)-iodo-terminated PMCP products. This enantioselective LCCTP process serves to establish access to readily available, practical, and scalable quantities of optically active liquid crystalline end-group-functionalized xPMCP building blocks for material science and technology discovery.