Twisted Cucurbit[14]uril
Twisted Cucurbit[14]uril
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扭曲葫芦[14]uril
DOI：
10.1002/anie.201210267
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发表时间：
2013-07-08
影响因子：
16.6
通讯作者：
Tao, Zhu
中科院分区：
文献类型：
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作者：
Cheng, Xiao-Jie;Liang, Li-Li;Tao, Zhu
自1981年Mock及其同事首次确定葫芦脲（Q [6]）的结构以来，在过去的三十年中，已经报道了一系列其同系物和衍生物。其同系物（例如Q [5]、Q [7]和Q [8]）是由Day和Kim在2000年发现的[2]，而葫芦[10]脲（Q [10]），其中包括一个Q [5]分子，是由Day在2002年报道的。[3]采用K2 S2 O 8直接氧化Q [n]物种的方法合成了过羟基化的（HO）2nQ [n]物种，实现了Q [n]物种的直接功能化。[4]近年来，Isaacs等人报道了一系列结构新颖的甘脲[5]和葫芦[n]脲衍生物的低聚物的制备，如倒葫芦[6]脲和倒葫芦[7]脲（iQ [6]和iQ [7]），[6]手性降开环-葫芦脲（N）-bis-ns-Q [6]，[7]和降开环-葫芦脲[10]（ns-Q [10]），这是由Q [10]中两个CH 2桥的形式挤出产生的。[8]这些新的葫芦[n]脲激发了对扩大的葫芦[n]脲家族的化学的进一步强烈兴趣。[9]有趣的是，Q [n]（n> 10）在反应混合物中被识别出来，[10]这些物种只在使用密度泛函理论的计算中被指出。[11]虽然Miyahara及其同事报道了一种大的半葫芦[12]脲[12]，但这并不显示典型的Q [n]性质。在此，我们报道了葫芦[n]脲家族的一个新成员，我们将其命名为tQ [14]。它是最大的葫芦[n]脲，由28个亚甲基桥连接14个正常甘脲单元。然而，它由14个单位的-甘脲-（CH 2）2-部分与3608扭转。因此，它不像大多数葫芦[n]脲那样有正常的空腔，
Since the structure of the cucurbituril (Q [6]), a cyclic oligomer of 6 units of glycoluril linked by 12 methylene bridges, was first determined by Mock and co-workers in 1981,[1] a series of its homologues and derivatives have been reported over the last three decades. The homologues (for example Q [5], Q [7], and Q [8]) were discovered by Day and Kim in 2000,[2] and cucurbit [10] uril (Q [10]), which includes a Q [5] molecule, was reported by Day in 2002.[3] The perhydroxylated (HO) 2nQ [n] species were synthesized by direct oxidation of Q [n] species with K2S2O8 and realized direct functionalization of the Q [n] species.[4] In recent years, Isaacs and co-workers reported the preparation of a series of oligomers of glycoluril [5] and cucurbit [n] uril derivatives with novel structures, such as the inverted cucurbit-[6] uril and inverted cucurbit [7] uril (iQ [6] and iQ [7]),[6] the chiral norseco-cucurbituril (Æ)-bis-ns-Q [6],[7] and the nor-seco-cucurbit [10] uril (ns-Q [10]), which results from formal extrusion of two CH2 bridges from Q [10].[8] These new cucurbit [n] urils have inspired further intense interest in the chemistry of the enlarged cucurbit [n] uril family.[9] Interestingly, Q [n](n> 10) was identified in reaction mixtures,[10] and these species have only been indicated in calculations by using the density functional theory.[11] Although Miyahara and co-workers have reported a large hemicucurbit [12] uril,[12] this does not show typical Q [n] properties.Herein, we report a new member of the cucurbit [n] uril family, which we name tQ [14]. It is the largest cucurbit [n] uril with 14 normal glycoluril units linked by 28 methylene bridges. However, it consists of 14 units of the-glycoluril-(CH2) 2-moiety with a 3608 twist. As a consequence, it does not have a normal cavity like the most cucubit [n] urils, and has