Steric-Stereoregular Polymers and Optically Active Helical Polymers/Achiral Reagent Complexes

这项工作的第一个目标是开发可再生的不对称还原聚合物试剂。试剂将是旋光性(手性)螺旋聚合物和硼烷的络合物。这些聚合物可以通过使用手性引发剂的活性阴离子聚合技术方便地合成。这种光学活性聚合物的一个例子是聚(甲基丙烯酸苯基-2-吡啶基-邻甲苯基甲基)。聚合物中2-吡啶基团的存在可以制备类似于聚(2-乙烯基吡啶)/硼烷络合物的光学活性聚合物/硼烷络合物。光学活性还原试剂将用于还原前手性羰基官能团。该项目的第二个目标是合成一类具有特殊二级结构的全同立构聚合物，即螺旋。要实现这一目标，首先要了解单体结构与全同立构聚合倾向之间的关系。本项目的起点将是聚(4-乙烯基喹啉)和聚(2-乙烯基萘)的合成和立体化学表征。这种具有特殊二级结构的全同立构聚合物或“立体-立体规则”聚合物有望在分子生物学、合成酶和可再生的不对称试剂中有潜在的应用。

The first objective of this work is to develop regenerable polymeric reagents for asymmetric reductions. The reagents will be complexes of optically active (chiral) helical polymers and borane. These polymers are conveniently synthesized by living anionic polymerization techniques using chiral initiators. An example of such an optically active polymer is poly (phenyl-2-pyridyl-o- tolylmethylmethacrylate). The presence of the 2-pyridyl groups in the polymer should allow for the preparation of the optically active polymer/borane complexes similar to poly (2-vinylpyridine)/borane complexes. The optically active reducing reagents will be used to reduce prochiral carbonyl functionalities. The second objective of the project is to synthesize a class of isotactic polymers which will exhibit specific secondary structures i.e. helix. This goal will be accomplished by first developing an understanding of the relationship between the structure of the monomer and the tendency to isotactic specific polymerization. The starting point of this project will be the synthesis and stereochemical characterization of poly (4-vinylquinoline) and poly (2-vinylnaphthalene). It is expected that such isotactic polymers with specific secondary structures or "steric-stereoregular" polymers will have potential applications in molecular biology, synthetic enzymes and regenerable asymmetric reagents.//