含手性侧链的1，7-二氮-12-冠-4的合成及其应用-物理化学专业论文.docxVIP

摘 摘 要 本文以二甘醇为起始原料，经过八步反应得到1，7一二氮一12一冠一4。 同时，通过手性氨基醇和氯乙酰氯作用可得到手性酰胺醇化合物，手性 酰胺醇和1、7一二氮一12-冠一4反应得到一类全新的手性冠醚 八个 含酰胺醇的手性冠醚。 通过手性氨基醇和原氯乙酸三乙酯反应得到手性嗯唑啉化合物，手 性嚼唑啉与1，7．二氮．12．冠一4反应得到另一类全新的手性冠醚配 体 八个手性嚼唑啉的手性冠醚配体。 利用毛细管电泳仪器，将本文合成的含酰胺醇的手性冠醚应用于 D，L．肉碱的手性拆分，取得了非常好的分离效果。 本文还从超分子化学角度对拆分体系中的分子之间的相互作用进 行了探讨。 另～方面，将本文合成的含曝唑啉手性冠醚配体的铜(II)配合物应 用于烯烃的不对称环丙烷化反应，其中对二苯乙烯的反应中，e．e．值达 到了28．8％左右；对苯乙烯的反应中，e．e．值达到了27．5％左右，取得 了较好的效果。 在配体合成和用于不对称催化反应的基础上，利用化学计算软件 优化和分析了本文所合成的含嗯唑啉手性冠醚配体的铜配合物的空间 构象，并对其进行了理论分析；并结合配合物的空间构象，解释了环丙 烷化反应机理， ABSTRACTIn ABSTRACT In this paper．we synthesized l，7一diaza-12一crown-4 with diglycol by eight steps· Then．Treatment of the chiral amino—alcohols with chloroacetyl chloride afforded the corresponding chiral N—chloroacetamido alcohols By reaction of 1．7-diaza一12。 crow33—4 with each of chiral N．chloroacetamido alcohols，a series of new chiral crowns were prepared．In this paper,eight chiral crowns containing N．chloroacetamido alcohols 【1,7一bis(4一alkyl-5一hydroxy一2一OXO一3一azapentyl)一1，7一 diaza一12一crown一4]were synthesized． Treatment of the amino-alcohols with triethyl orthochloroacetate afforded the corresponding 2-chloromethyl一4一alkyl一2-oxazolines．By reaction of 1,7-diaza一12- crown-4 with each of chiral oxazolines，another series of new chiral crown ligands were prepared．In this paper,eight mulfidentate ligands containing oxazolines [1，7一bis(4一alkyloxazolin一2-yl-methyl)一1，7一diaza·12一crown-4]were synthesized． By the capillary electrophoresis，the chiral crowns containing N— chloroacetamido alcohols were used in the chiral separation of d，1-camitine，the results were satisfactory．Furthermore．the mechanism of chiral separation was also studied by supramolecular chemistry． The Cu(II)complexes of chiral crowns containing containing oxazolines were used as enantioselective catalysts in the asymmetric cyclopropanation reactions of l，1一diphenylethylene and styrene．A moderate optical yield(~28．8％)was achieved when they used in the reaction of 1，1-diphenylethylene，27．5％was achieved in