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

以香草醇为原料，通过1，5-二[(4-羟甲基)-2-甲氧基苯氧基]-3-氧并戊烷的直接三聚和/或分步反应合成了反式和合二乙氧基桥联隐丹(1a和1b)。与反异构体(1a)相比，合成异构体(1b)对铯、碱金属阳离子中的四乙基铵和三乙基甲基铵阳离子具有较高的选择性络合能力。我们还成功地合成了几个芳香族桥联隐丹。以α，α‘-双[4-羟甲基-2-甲氧基苯氧基]-对二甲苯为原料，采用直接三聚法合成了对二甲苯桥联隐语反2a。以香草醇为原料，采用直接三聚法和/或分步法合成了邻二甲苯桥联隐丹抗-3a。以香草醇为原料，采用分步法合成了o-[4，5-双(甲氧羰基)]二甲苯桥联隐语化合物anti-4a和syn-4b。反二甲苯桥联隐语(2和3)能与一、二、三、季铵盐阳离子中几乎所有的季铵盐阳离子络合，并选择性地以Net_3Me~+为客体络合。从邻二甲苯桥联隐语化合物anti-3a及其类似物anti-4a和syn-4b与NME_4~+阳离子的络合反应来看，证实了化合物anti-3a和syn-4b与客体阳离子的络合作用，但没有证实含有anti-4a。考察了隐丹与正己烷、正庚烷、正辛烷等几种异构体的络合能力。与对映异构体(1b-3b)相比，合成异构体(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).