Synthesis of Chiral Polymers Including Cyclic Imide Structures By Asymmetric Polymerization and Optical Resolution Using their Polymers

通过不对称聚合合成包含环状酰亚胺结构的手性聚合物并使用其聚合物进行光学拆分

• 批准号: 15550108
• 负责人: OISHI Tsutomu
• 金额: $ 2.3万
• 依托单位: Yamaguchi University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550108/
• 关键词: Optically Active Polymer; Asymmetric Polymerization; Maleimide Derivatives; Optical Resolution; Atom Transfer Radical Polymerization; Chiral Polymer; Chiral Stationary Phase; HPLC; キラルリガンド; イタコンイミド; 分子認識; N-置換マレイミド; 有機金属; 理論計算

Asymmetric polymerization of N-substituted maleimide (RMI) and N-substituted itaconimide (RII) were performed with chiral ligand/organometal complexes as an initiator. The polymerizabilities of the monomers, chiroptical properties of polymers and optical resolution of the polymers were investigated. Precision asymmetric radical polymerizations of RMI were carried out to find living radical and stereo-specific polymerization abilities. The results are shown as follows :1.Asymmetric Radical Polymerization and Atom Transfer Radical Polymerization (ATRP) of RMI : The ATRP of N-1-phenylethylmaleimide, N-naphthyl maleimide (NMI) and N-phenyl maleimide were performed to obtain chiral polymers. However, the living radical polymerization character was not observed. The radical polymerization of NMI using chiral cobalt complex gave chiral NMI polymers with relatively high specific rotations.2.Asymmetric Polymerization of Chiral RMI and Optical Resolution of Their Polymers : RMI including amino a … More cid derivatives, i.e., L-alanine, L-leucine, L-valine, (R) or (S)-phenylalanine and (R) or (S) phenylglycine, were synthesized and polymerized anionically using chiral ligand and organometal complex to obtain polymers with high specific rotations. Asymmetric induction onto the polymer main chain took place judging from the circular dichroism (CD) and NMR spectra. Chiral stationary phases (CSP) for HPLC were prepared from silica gel and the polymers. The coated type CSP can resolve some racemic compounds.3.Preparation of Chemically Bonded CSP : Chemically bonded CSPs for HPLC were prepared from silica gel and the polymers to find the possibility of optical resolution. Some of the CSPs can resolve racemic compounds completely and can be used in all solvents.4.Synthesis and Asymmetric Polymerization of Novel RMI : Some novel types of RMI having an azacrown-ether or an acetylene derivative as N-substituent were synthesized and polymerized. The polymerization properties of the monomers and chiroptical properties of the polymers were investigated by NMR and CD spectra.5.Synthesis and Asymmetric Polymerization of Novel RII : Some new types of RII containing amino acid derivatives were synthesized and polymerized with chiral ligand and organometals complex to give chiral polymers. Chiroptical and optical resolution properties of the polymers were investigated. Less

以手性配体/有机金属配合物为引发剂，进行了n -取代马来酰亚胺（RMI）和n -取代伊塔克酰亚胺（RII）的不对称聚合。研究了单体的可聚合性、聚合物的旋热性能和聚合物的光学分辨率。对RMI进行了精确的不对称自由基聚合，以发现活性自由基和立体特异性聚合能力。研究结果如下：1。RMI的不对称自由基聚合和原子转移自由基聚合（ATRP）：通过n -1-苯基乙基马来酰亚胺、n -萘基马来酰亚胺和n -苯基马来酰亚胺的不对称自由基聚合（ATRP）得到了手性聚合物。但未观察到活性自由基聚合的特征。用手性钴配合物对NMI进行自由基聚合，得到了具有较高比旋率的手性NMI聚合物。利用手性配体和金属有机配合物，合成了l -丙氨酸、l -亮氨酸、l -缬氨酸、(R)或(S)-苯丙氨酸和(R)或(S)-苯甘氨酸等多酸类衍生物，并进行阴离子聚合，得到了具有高比旋的聚合物。从圆二色性和核磁共振光谱来看，聚合物主链发生了不对称感应。以硅胶和聚合物为原料制备了高效液相色谱用手性固定相。包覆型CSP可以溶解一些外消旋化合物。化学键合CSP的制备：以硅胶和聚合物为原料制备了用于高效液相色谱的化学键合CSP，以寻找光学分辨的可能性。有些csp能完全分解外消旋化合物，并能在所有溶剂中使用。新型RMI的合成和不对称聚合：合成了一些以氮冠醚或乙炔衍生物为n取代基的新型RMI。用核磁共振和CD谱研究了单体的聚合性能和聚合物的共热性能。新型RII的合成与不对称聚合：合成了几种含氨基酸衍生物的新型RII，并与手性配体和有机金属配合物进行了聚合，得到了手性聚合物。研究了聚合物的热学和光学分辨性能。少

项目成果

Asymmetric polymerization of N-1-naphthylmaleimide with (R, R)-N, N-bis(3, 5-di-tert-butylsalicylidene)1, 2-cyclohe xanediaminatocobalt (II)

N-1-萘基马来酰亚胺与(R,R)-N,N-双(3,5-二叔丁基水杨基)1,2-环己二胺钴(II)的不对称聚合

• 发表时间: 2004
• 期刊: Journal of Polymer Science Part A : Polymer Chemistry 42・23
• 作者: Tsutomu Oishi;Kenjiro Onimura;Tsutomu Oishi;Kenjiro Onimura;Lee Y. -K
• 通讯作者: Lee Y. -K

Polycondensation of Chiral 3, 4-Dihydro-N-Substituted Succinimide and Phthalic Acid Dichloride

手性3, 4-二氢-N-取代琥珀酰亚胺与邻苯二甲酰二氯的缩聚反应

• 发表时间: 2003
• 期刊: Polymer Bulletin 50
• 作者: Yuan Zhang;Kenjiro Onimura;Hiromoni Tsutsumi;Tsutomu Oishi;Lee Y.-K;Tsutomu Oishi;Kenjiro Onimura
• 通讯作者: Kenjiro Onimura

Asymmetric Anionic Polymerization of (S)-(−)-N-Maleoyl-L-Valine Methyl Ester

• DOI: 10.1295/polymj.36.878
• 发表时间: 2004-11
• 期刊: Polymer Journal
• 影响因子: 2.8
• 作者: Y. Zhang;K. Onimura;H. Tsutsumi;T. Oishi

Theoretical study on the polymerization mechanism of substituted maleimides by using a chiral catalyst with Zn2+

• DOI: 10.1016/s0040-4020(03)01014-7
• 发表时间: 2003-08-11
• 期刊: TETRAHEDRON
• 影响因子: 2.1
• 作者: Hori, K;Yoshimura, K;Oishi, T
• 通讯作者: Oishi, T

Tsutomu Oishi: "Asymmetric Polymerization of N-ortho or para-Substituted Phenylmaleimide Using Chiral Anionic Initiator"Polymer Journal. 35. 245-254 (2003)

Tsutomu Oishi：“使用手性阴离子引发剂进行 N-邻位或对位取代的苯基马来酰亚胺的不对称聚合”聚合物杂志。