侧链带有L-氨基酸乙酯的螺旋聚苯乙炔衍生物的手性识别能力研究
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摘要
采用Rh(nbd)BPh4催化剂合成了3种侧链带有L-氨基酸乙酯的螺旋聚苯乙炔衍生物PPA-S-Phe、PPA-S-Leu和PPA-A-Leu,并将其涂覆在氨丙基硅胶上制备高效液相色谱(HPLC)手性固定相(CSP),研究其对7种对映体的手性识别能力.由于侧链手性基团或主链与手性基团之间的链接基团不同,PPA-S-Phe、PPA-S-Leu和PPA-A-Leu形成了不同的螺旋构象,并表现出对对映体不同的手性识别能力.PPA-S-Phe和PPA-S-Leu的主链与手性基团之间的链接基团均为磺酰胺基,侧链手性基团为L-亮氨酸乙酯的PPA-S-Leu的手性识别能力优于侧链手性基团为L-苯丙氨酸乙酯的PPA-S-Phe.PPA-S-Leu和PPA-A-Leu的侧链手性基团均为L-亮氨酸乙酯,以酰胺基为链接基团的PPA-A-Leu的手性识别能力明显优于以磺酰胺基为链接基团的PPA-S-Leu.螺旋聚苯乙炔主链与侧链手性基团之间的链接基团、侧链手性基团在手性识别中均发挥十分着重要作用.
Three one-handed helical poly(phenylacetylene) derivatives bearing L-amino acid ethyl ester pendants,PPA-S-Phe,PPA-S-Leu and PPA-A-Leu were respectively synthesized by the polymerization of the corresponding monomers using Rh(nbd)BPh4 as a catalyst,and their chiral recognition abilities for seven racemates were evaluated as chiral stationary phases(CSPs) for high-performance liquid chromatography(HPLC) after coating them on silica gel.The difference between PPA-S-Phe and PPA-S-Leu is the chiral pendants.The chiral pendant of PPA-S-Phe is L-phenylalanine ethyl ester,while that of PPA-S-Leu is L-leucine ethyl ester.The difference between PPA-S-Leu and PPA-A-Leu is the linkage groups between polymer main chains and chiral pendants.The linkage of PPA-S-Leu is sulphonamide group,while that of PPA-A-Leu is amide group.PPA-S-Phe,PPA-S-Leu and PPA-A-Leu possess their characteristic helical conformation and show their characteristic chiral recognition depending on the chiral pendants and the linkage groups.When linkage is a sulphonamide group,PPA-S-Leu with L-leucine ethyl ester pendants shows higher chiral recognition abilities than PPA-S-Phe with L-phenylalanine ethyl ester pendants.When chiral pendant is L-leucine ethyl ester,PPA-A-Leu with amide linkage shows higher chiral recognition abilities than PPA-S-Leu with sulphonamide linkage.It is concluded that the linkage groups play an important role in chiral recognition as well as the chiral pendants.
Three one-handed helical poly(phenylacetylene) derivatives bearing L-amino acid ethyl ester pendants,PPA-S-Phe,PPA-S-Leu and PPA-A-Leu were respectively synthesized by the polymerization of the corresponding monomers using Rh(nbd)BPh4 as a catalyst,and their chiral recognition abilities for seven racemates were evaluated as chiral stationary phases(CSPs) for high-performance liquid chromatography(HPLC) after coating them on silica gel.The difference between PPA-S-Phe and PPA-S-Leu is the chiral pendants.The chiral pendant of PPA-S-Phe is L-phenylalanine ethyl ester,while that of PPA-S-Leu is L-leucine ethyl ester.The difference between PPA-S-Leu and PPA-A-Leu is the linkage groups between polymer main chains and chiral pendants.The linkage of PPA-S-Leu is sulphonamide group,while that of PPA-A-Leu is amide group.PPA-S-Phe,PPA-S-Leu and PPA-A-Leu possess their characteristic helical conformation and show their characteristic chiral recognition depending on the chiral pendants and the linkage groups.When linkage is a sulphonamide group,PPA-S-Leu with L-leucine ethyl ester pendants shows higher chiral recognition abilities than PPA-S-Phe with L-phenylalanine ethyl ester pendants.When chiral pendant is L-leucine ethyl ester,PPA-A-Leu with amide linkage shows higher chiral recognition abilities than PPA-S-Leu with sulphonamide linkage.It is concluded that the linkage groups play an important role in chiral recognition as well as the chiral pendants.
引文
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3 Ikai T,Okamoto Y.Chem Rev,2009,109:6077～6101
4 Okamoto Y,Ikai T.Chem Soc Rev,2008,37:2593～2608
5 Stringham R W.Adv Chromatogr,2006,44:257～290
6 Okamoto Y,Ikai T,Shen J.Isr J Chem,2011,51:1096～1106
7 Lai X,Tang W,Ng S C.J Chromatogr A,2011,1218:3496～3501
8 Morioka K,Suito Y,Isobe Y,Habaue S,Okamoto Y.J Polym Sci,Part A:Polym Chem,2003,41:3354～3360
9 Liu Guangxuan(刘光烜),Lu Wei(路伟),Jiang Liming(江黎明),Sun weilin(孙维林),Shen Zhiquan(沈之荃),Wang Yukang(王玉康).Acta Polymerica Sinica(高分子学报),2009,(8):775～780
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14 Miyabe T,Iida H,Ohnishi A,Yashima E.Chem Sci,2012,3:863～867
15 Teraguchi M,Suzuki J,Kaneko T,Aoki T,Masuda T.Macromolecules,2003,36:9694～9697
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19 Kakuchi R,Kodama T,Shimada R,Tago Y,Sakai R,Satoh T,Kakuchi T.Macromolecules,2009,42:3892～3897
20 Kishimoto Y,Itou M,Miyatake T,Ikariya T,Noyori R.Macromolecules,1995,28:6662～6666
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