Syntheses of cryptophanes and their molecular recognition toward achira and chiral molecules

以香兰醇为原料，分别以1,5-二[（4-羟甲基）-2-甲氧基苯氧基]-3-奥戊烷为直接三聚体和/或分步法制备了反二乙烯氧基和顺二乙烯氧基桥接隐烷（1a和1b）。与反同分异构体（1a）相比，同分异构体（1b）对所研究的碱金属和烷基铵阳离子中的铯、四乙基铵和三乙基甲基铵阳离子具有高度的选择性络合能力。还成功地合成了几种芳香桥接隐烷。采用α， α′-双[4-羟甲基-2-甲氧基苯氧基]-对二甲苯直接三聚法制备了对二甲苯桥接的隐烷抗-2a。以香兰醇为原料，采用直接三聚法和/或分步法合成邻二甲苯桥接隐烷抗-3a。以香草醇为原料，采用分步法制备了o-[4,5-双（甲氧基羰基）]二甲苯桥接的隐烷抗-4a和syn-4b。抗二甲苯桥接隐烷（2和3）能与伯、仲、叔、季铵阳离子中几乎所有的季烷基铵阳离子络合，并选择性地与NEt_3Me^+阳离子络合。从邻二甲苯桥接的隐烷抗-3a及其类似物抗-4a和syn-4b与NMe_4^+阳离子的络合反应可以确定隐烷抗-3a和syn-4b与客体阳离子的络合反应，但未确定其是否包含抗-4a。并研究了隐烷、1、2和3与几种正己烷、庚烷和辛烷异构体的络合能力。与反异构体（1b-3b）相比，正异构体（1b-3b）对几种烷烃具有选择性络合能力。

The anti-and syn-diethyleneoxy bridged cryptophanes (1a and 1b) were prepared by the direct trimerization of 1,5-bis [(4-hydroxymethyl) -2-methoxyphenoxy] -3-oxapentane and/or by stepwise methods from vanillyl alchohol. The syn-isomer (1b) showed highly selective complexing abilities for cesium, and the tetraethylammonium and triethylmethylammonium cations among the investigated alkali metal and alkyl ammonium cations as compared with those of the anti-isomer (1a). Several aromatic bridged cryptophanes were also successfully synthesized. p-Xylene bridged cryptophane anti-2a was prepared by the direct trimerization of alpha, alpha'-bis [4-hydroxymethyl-2-methoxyphenoxy] -p-xylene. The synthesis of o-xylene bridged cryptophane anti-3a was carried out by the direct trimerization and/or the stepwise method from vanillyl alcohol. The o- [4,5-bis (methoxycarbonyl)] xylene bridged cryptophanes anti-4a and syn-4b were also prepared by the stepwise method from vanillyl alcohol. Anti-xylene bridged cryptophanes (2 and 3) was capable of complexing with almost all the quaternary alkylammonium cations among the primary, secondary, tertiary and quaternary ammonium cations, and selectively prefered to complex with NEt_3Me^+ cation as a guest. From the complexation of the o-xylene bridged cryptophane anti-3a and the analogs anti-4a and syn-4b with the NMe_4^+ cation, the cryptophanes anti-3a and syn-4b were confirmed to complex with the guest cation, however, anti-4a was not confirmed to be included. Also complexing abilities of cryptophanes, 1,2 and 3 with several kind of isomers of hexane, heptane and octane were investigated. The syn isomers (1b-3b) showed selective complexing abilities for several alkanes as compared with those of the anti isomers (1b-3b).