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

用于光学活性化合物分离的光学活性螺旋聚合物材料的制备

• 批准号: 06555279
• 负责人: ITO Yoshihiko
• 金额: $ 8.13万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06555279/
• 关键词: Helical Poly (quinoxaline) s; Optically Active Poly (quinoxaline) s; Helical Polymers; 1,2-Diisocyanobenzene; Screw Sense Selective Polymerization; Stereoselective Polymerization; Asymmetric Polymerization; ポリ(キノキサリン); 螺旋ポリ(キノキサリン); ポリキノキサリン; らせ

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.

3，6-二(对甲苯基)-1，2-二异氰苯在反甲基钯(II)双(二甲基苯基膦)络合物的诱导下聚合，得到具有螺旋结构的聚[5，8-二(对甲苯基)-2，3-喹恶啉]S。在具有手性膦配体P^*=[(S)-2-甲基]_2PPh的反式-MePdBrP_2^*催化的1，2-二异氰基-3，6-二(对甲苯基)苯的齐聚反应中，一对[Quinque(喹恶啉-2，3-二基)]钯(II)膦(II)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，一个基于Quinque(喹恶啉-2，3-二基)主链的螺旋性，另一个基于膦配体的螺旋性。两种非对映异构体纯钯(II)配合物(M，S)和(P，S)-配合物均能诱导3，6-二(对甲苯基)-1，2-二异氰苯的螺旋选择性聚合，并延长了起始钯(II)配合物的螺旋构象。2‘-甲氧基-1，1’-联苯基-2-碘与钯(0)三(二甲基苯基)膦配合物合成了光学活性的2‘-甲氧基-1，1’-联苯基-2-钯(II)-碘双(二甲基苯基膦)配合物，催化了3，6-二(对甲苯基)-1，2-二异氰苯的聚合，但立体选择性较低。相反，3，6-二(对甲苯基)-1，2-二异氰苯在光学活性的1，1‘-联苯并2-钯(II)双(二甲基苯基膦)络合物催化剂作用下实现了螺旋传感选择性聚合。

项目成果

Yoshihiko Ito: "New Synthesis of Quinoxaline Derivatives Based on Palladium Catalyzed Oligomerization of 1,2-Diisocyanoarenes" Heterocycles. Vol.42. 597-615 (1996)

Yoshihiko Ito：“基于钯催化 1,2-二异氰基芳烃齐聚的喹喔啉衍生物的新合成”杂环。

Yoshihiko Ito: "New Synthesis of Quinoxaline Derivatives Based on Palladium Catalyzed Oligomerization of 1,2-Diisocyanoarenes" Heterocycles. 42. 597-615 (1996)

Yoshihiko Ito：“基于钯催化 1,2-二异氰基芳烃齐聚的喹喔啉衍生物的新合成”杂环。

Yoshihiko Ito: "Screw-Sense Selective Polymerization of 3,6-Di(p-tolyl)-1,2-diisocyanobenzene Catalyzed by Optically Active 2-Binaphtyl palladium(II) Iodide Bis(dimethylphenylphosphine)Complex" JACS. (in press).

Yoshihiko Ito：“光学活性 2-联萘基钯 (II) 碘化物双（二甲基苯基膦）络合物催化 3,6-二（对甲苯基）-1,2-二异氰基苯的螺杆选择性聚合”JACS。

Yoshihiko Ito: "Screw-Sense Selective Polymerization of 3,6-Di (p-tolyl) -1,2-diisocyanobenzene Catalyzed by Optically Active 2-Binaphtyl palladium (II) Iodide Bis (dimethylphenyl-phosphine) Complex" JACS. (in press).

Yoshihiko Ito：“光学活性 2-联萘基钯 (II) 碘化物双（二甲基苯基膦）络合物催化 3,6-二（对甲苯基）-1,2-二异氰基苯的螺杆选择性聚合”JACS。