Preparation of Optically Active Helical Polymer Materials for Separation of Optically Active Compounds

用反式甲基溴化钯双（二甲基苯基膦）配合物引发3，6-二（对甲苯基）-1，2-二异氰酸苯聚合，得到了具有螺旋结构的聚[5，8-二（对甲苯基）-2，3-喹喔啉]。在具有手性膦配体P ^*=[（S）-2-甲基]_2PPh的trans-MePdBrP_2 ^* 诱导的1，2-二异氰基-3，6-二（对甲苯基）苯的齐聚反应中，[五甲基]对映异构体由此制备的[（喹喔啉-2，3-二基）]钯（II）膦配合物已被分离成相应的具有两个手性元素的（M，S）-和（P，S）-配合物，一种是基于喹（喹喔啉-2，3-二基）骨架的螺旋性，另一种是膦配体。两种非对映体纯的钯（II）配合物（M，S）-和（P，S）-配合物均诱导了3，6-二（对甲苯基）-1，2-二异氰苯的螺旋选择性聚合，并使起始钯（II）配合物的螺旋构象扩展。由2 ′-甲氧基-1，1 ′-联萘基-2-碘化钯（II）与钯（O）-三（二甲基苯基膦）配合物反应，合成了光学活性的2 ′-甲氧基-1，1 ′-联萘基-2-碘化钯（II）-双（二甲基苯基膦）配合物。相反，3，6-二（对甲苯基）-1，2-二异氰酸苯的螺旋定向选择性聚合通过光学活性的1，1'-联萘基-2-碘化钯（II）双（二甲基苯基膦）络合物催化剂实现。

Polymerization of 3,6-di (p-tolyl) -1,2-diisocyanobenzene was induced by trans-methyl-palladium (II) bromide bis (dimethylphenylphosphine) complex to give poly [5,8-di (p-tolyl) -2,3-quinoxaline] s, which have helical structures. In an oligomerization of 1,2-diisocyano-3,6-di (p-tolyl) benzene induced by trans-MePdBrP_2^* having chiral phosphine ligands P^*= [ (S)-2-methyl] _2PPh, a diastereomeric pair of [quinque (quinoxaline-2,3-diyl) ] palladium (II) phosphine complexes thus prepared have been separated to the corresponding (M,S) -and (P,S) -complexes having two chiral elements, one based on the helicity of the backbone of quinque (quinoxaline-2,3-diyl) and the other of the phosphine ligands. Both diastereomerically pure palladium (II) complexes, (M,S) -and (P,S) -complexes, induced a screw-sense selective polymerization of 3,6-di (p-tolyl) -1,2-diisocyanobenzene with the extension of the helical conformation of the starting palladium (II) complexes. Optically active 2'-methoxy-1,1'-binaphtyl-2-palladium (II) -iodide bis (dimethylphenylphosphine) complex, which was been prepared by the reaction of 2'-methoxy-1,1'-binaphtyl-2-iodide with palladium (0) tris (dimethylphenylphosphine) complex, induced the polymerization of 3,6-di (p-tolyl) -1,2-diisocyanobenzene in good yield, but in low stereoselectivity. In contrast, a screw sense selective polymerization of 3,6-di (p-tolyl) -1,2-diisocyanobenzene was achieved by optically active 1,1'-binaphtyl-2-palladium (II) iodide bis (dimethylphenylphosphine) complex catalyst.