CAJ | 학술논문

提出了一种采用谷氨酸席夫碱Ni(Ⅱ)配合物共保护L-谷氨酸的α-氨基和α-羧基合成γ-L-谷氨酰二肽的新方法.首先由手性助剂--2-[N-(N-苄基-脯氨酰)氨基]二苯甲酮(1)、六水合氯化镍和L-谷氨酸反应,得到谷氨酸席夫碱Ni(Ⅱ)配合物2,产率为98.2%;进而采用二异丙基碳二亚胺(DIC)/1-羟基-苯并三唑(HOBt)复合缩合剂法分别与L-氨基酸3a～3h反应,得到相应的γ-L-谷氨酰二肽席夫碱Ni(Ⅱ)配合物4a～4h,产率为93.1%～99.0%;最后稀酸水解配合物,得到γ-L-谷氨酰二肽5a～5h,产率为73.0%～86.4%,高收率[92.2%～97.4%)回收手性助剂.中间产物和终产物的结构经由旋光,~1H NMR,~(13)C NMR和HRMS表征.
제출료일충채용곡안산석부감Ni(Ⅱ)배합물공보호L-곡안산적α-안기화α-최기합성γ-L-곡안선이태적신방법.수선유수성조제--2-[N-(N-변기-포안선)안기]이분갑동(1)、륙수합록화얼화L-곡안산반응,득도곡안산석부감Ni(Ⅱ)배합물2,산솔위98.2%;진이채용이이병기탄이아알(DIC)/1-간기-분병삼서(HOBt)복합축합제법분별여L-안기산3a～3h반응,득도상응적γ-L-곡안선이태석부감Ni(Ⅱ)배합물4a～4h,산솔위93.1%～99.0%;최후희산수해배합물,득도γ-L-곡안선이태5a～5h,산솔위73.0%～86.4%,고수솔[92.2%～97.4%)회수수성조제.중간산물화종산물적결구경유선광,~1H NMR,~(13)C NMR화HRMS표정.
A novel method for the synthesis of γ-Z-glutamyl dipeptides via a Ni(Ⅱ) complex of glutamic acid Schiff base, which has been employed as co-protection of the a-amino and a-carboxyl groups of L-glutamic acid, was described. Firstly, a Ni(Ⅱ) complex 2 of glutamic acid Schiff base was formed in a yield of 98.2% from chiral auxiliary 2-[N-(N-benzyl-prolyl)amino]benzopheone (1) with nickel(Ⅱ) chloride hexahydrate and L-glutamic acid. Then, 2 was reacted separately with L-amino acids 3a～3h to give Ni(Ⅱ) complexes 4a～4h of γ-L-glutamyl dipeptide Schiff base in yields of 93.1%～99.0% using a DIC/HOBt coupling method. Finally, after decomposition of the complexes 4a～4h with aqueous HC1, γ-L-glutamyl dipeptides 5a～5h were obtained in yields of 73.0%～86.4% and the chiral auxiliary 1 was recovered in high yields of 92.2%～97.4%, respectively. The structures of intermediates and final products were characterized by optical rotation, ~1H NMR, ~(13)C NMR and HRMS techniques.