新型手性N,N′-双支套索冠醚的合成及其应用

(S)-苯丙氨醇和原氯乙酸三乙酯作用得到的手性酰胺醇和手性噁唑啉分别与1,7-二氮-12-冠-4反应, 得到了两种手性N,N′-双支套索冠醚N,N′-二[(S)-N-(1-羟甲基-2-苯基乙基)乙酰胺-2]-1,7-二氮-12-冠-4 (1a)和N,N′-二[(S)-4-苄基-噁唑啉-2-亚甲基]-1,7-二氮-12-冠-4 (1b). 前者应用于D/L-肉碱的手性分离; 后者的铜配合物用于重氮醋酸酯对烯烃的不对称环丙烷化反应.

Synthesis of New N,N''''-Bichiral Lariat Crown Ethers and Their Application

Two N,N′-bichiral lariat crown ethers, (S,S)-1,7-bis(4-benzyl-5-hydroxy-2-oxo-3-azapentyl)-1,7- diaza-12-crown-4 (1a) and (S,S)-1,7-bis(4-benzyloxazolin-2-yl-methyl)-1,7-diaza-12-crown-4 (1b), were obtained by alkylation of 1,7-diaza-12-crown-4 with (S)-(1-hydroxy-3-phenylprop-2-yl)-chloroacetamide or (S)-2-chloromethyl-4-benzyloxazoline, which were obtained by the reaction of (S)-2-amino-3-phenylpro- panol with triethyl orthochloroacetate. 1a was used successfully in the chiral separations of D/L-carnitine by capillary zone electrophoresis. Cu(II) complex of 1b was applied to the asymmetric cyclopropanation of 1,1-diphenylethylene with alkyl diazoace-tate.