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

用反式甲基溴化钯（II）双（二甲苯基膦）络合物聚合3,6-二（对苯基）-1,2-二异氰苯，得到具有螺旋结构的聚[5,8-二（对苯基）-2,3-喹啉]5。在具有手性膦配体P^*= [(S)-2-甲基]_2PPh的反式mepdbrp_2 ^*诱导1,2-二异氰酸钠-3,6-二（对苯基）苯的寡聚反应中，制备的[醌（喹啉-2,3-二基）]钯（II）膦配合物被分离成相应的具有两个手性元素的（M，S）和（P，S）配合物，其中一个是基于醌（喹啉-2,3-二基）骨架的螺旋性，另一个是基于膦配体。非对映异构纯钯（II）配合物（M，S）和（P，S） -配合物随着起始钯（II）配合物螺旋构象的扩展，诱导3,6-二（对甲苯）-1,2-二异氰苯的螺旋选择性聚合。2′-甲氧基-1,1′-联萘基-2-钯(II) -碘二（二甲基苯基膦）配合物与钯(0)三（二甲基苯基膦）配合物反应制备了光学活性的2′-甲氧基-1,1′-联萘基-2-钯(II) -碘二（二甲基苯基膦）配合物，诱导了3,6-二（对苯基）-1,2-二异氰基苯的聚合，收率高，但立体选择性低。以旋光性1,1′-联萘基-2-碘化钯(II) -二（二甲苯基膦）配合物为催化剂，实现了3,6-二（对甲苯）-1,2-二异氰苯的螺旋选择性聚合。

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.