采用谷氨酸席夫碱Ni(Ⅱ)配合物法合成L-茶氨酸。手性助剂——2-[N-(N-苄基)-脯氨酰]-氨基-二苯甲酮(BPB)、六水合氯化镍和L-谷氨酸反应,将谷氨酸的α-羧基和氨基进行同时保护,得到谷氨酸席夫碱Ni(Ⅱ)配合物;通过接肽试剂与乙胺盐酸盐反应,得到茶氨酸席夫碱Ni(Ⅱ)配合物,经酸水解后离交分离,获得L-茶氨酸,3步反应总收率为70%。手性辅基BPB可回收,回收率超过9HD%。中间产物和终产物的结构经由^1HNMR、HRMS和旋光表征。
L-Theanine was synthesized via Ni ( Ⅱ ) complex of glutamic acid' s Schiff base. Through reacting with chiral auxiliary 2- [ N- (N'-benzyl-prolyl) amino ] benzophenone and NiCl2, the α- carboxyl and amino groups of L-glutamic acid were co-protected as Schiff base. After amidation reaction, the complex of L-theanine's Schiff base was formed. Finally, L-theanine was obtained in an overall 70% yield by hydrolysis of the complex and separation of hydrolyzed mixtures in an ion exchanger column. The chiral auxiliary could be recovered in a yield exceeding 90%. Structures of intermediates and final products were characterized by ^1HNMR, HRMS and optical rotation measurements.