【作者】 吴划方；

【导师】 潘鑫复； 张国林；

【作者基本信息】 兰州大学 ， 有机化学， 2008， 博士

【摘要】 本论文主要对链状L-氨基酸的N-手性季铵盐进行了研究,包括N-手性季铵盐的合成、分离、N-手性绝对构型的确定,并对它们的稳定性等进行了考察。本论文包括三部分:◆N-手性季铵盐的合成及其在有机合成中的应用(综述)本文对N-手性的发现、N-手性季铵盐的合成、分离、绝对构型确定及其在有机合成中应用进行了简要综述。◆链状L-氨基酸的N-手性季铵盐的合成、分离、及绝对构型确定对合成叔胺的“一锅法”进行了改进,并成功合成了12对新的链状和环状N-手性季铵盐。采用手性联萘酚包结拆分法、重结晶法、沉淀法等成功地对其中9对N-手性季铵盐的非对映异构体混合物进行了分离,通过X-单晶衍射确定了其中16个N-手性季铵盐中N的绝对构型。◆N-手性季铵盐的取代反应、不对称催化及稳定性研究链状L-氨基酸合成N-手性季铵盐过程中发现的N上基团被烯丙基取代现象为首次发现。对反应进行了初步考察,其过程是先生成了预期的季铵盐,随后这个季铵盐中的基团又被烯丙基溴取代。初步实验表明,底物中带有甲氧羰基及卤代烃为烯丙基溴对于此取代现象是必要的。初步实验表明,我们所合成的N-手性季铵盐显示出一定程度不对称催化作用,但是选择性不高;所合成的N-手性季铵盐对光、热及酸碱稳定,未发现消旋化。更多还原

【Abstract】 This dissertation aims at the studies on N-chiral quaternary ammonium salts （QASs）of linear L-amino acid,including the syntheses,separation,the absolute configuration determination of N-chirality,and their stablity.It consisted of the following three parts:The syntheses and applications of N-chiral QASs in organic syntheses （Riview）Described the finding,syntheses,separation,the absolute configuration determination and applications of N-chiral QASs in organic syntheses.Studies on N-chiral QASs of linear L-amino acid,including the syntheses, separation,the absolute configuration determination of N-chirality.We synthesized tertiary amine using improved“one pot”method from linear L-amino acid,and synthesized twelve paries of linear and cyclic N-chiral QASs successfully.We separated nine pairs of these QASs diastereomers through resolution by chiral BINOL,recrystallization,precipitation and determined the absolute configuration of N-chirality by X-ray single crystallographic analysis for sixteen of them.Studties on the substitute reaction,asymmetric catalyzed reaction and the stability of N-chiral QASsIn the course of synthesis of N-chiral QASs from L-amino acids,when the tertiary amine with a methoxycarbonyl group refluxed with allyl bromide in CH₃CN, diallyl substitued QASs were obtained instead of the expected N-chiral QASs.We studied the reaction conditions such as various substrates,temperature,halogenated hydrocarbon.We believe that the required N-chiral QASs were formed firstly,then they reacted with allyl bromide quickly to obtain the diallyl substitued QASs.The preliminary experiments indicated that the tertiary amine with a methoxy car-bonyl group and the allyl bromide are necessary for the substitute.The preliminary experiment indicated that the N-chiral QASs have a certain extent asymmetric catalyzed activity,but the selectivity is not high.There is no racemization when N-chiral QASs under light,hot,acid and base更多还原