A Facile and Efficient Preparation of Pillararenes and a Pillarquinone
A Facile and Efficient Preparation of Pillararenes and a Pillarquinone
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DOI：
10.1002/anie.200904765
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发表时间：
2009-01-01
影响因子：
16.6
通讯作者：
Meier, Herbert
中科院分区：
文献类型：
--
作者：
Cao, Derong;Kou, Yuhui;Meier, Herbert
杯芳烃1及其衍生物在过去的二十年中引起了相当大的关注。这种关注可以归因于它们在气体吸附，[1]纳米管，[2]催化，[3] DNA识别[4]和富勒烯化学等领域的应用。[5]近年来，在超分子化学中，人们开发了许多杯芳烃类似物，如杯吡咯[6]、硫杂杯芳烃[7]和高氧杂杯芳烃。[8]与关于间位桥连环状低聚物1的大量文献相反，对其对位桥连类似物2（称为柱[n]芳烃）知之甚少（方案1）。最近，该系列的前两个成员2n（n= 5，R= OCH 3，OH）被报道。[9]它们表现出非常有趣的主-客体性质，但它们的制备相当繁琐;刘易斯酸催化的1，4-二甲氧基苯和多聚甲醛的缩合反应生成含有一些环状五聚体25（R= OCH 3）的聚合物。用BBr 3进行醚裂解得到具有游离羟基25（R= OH）的柱[5]芳烃。各个步骤的产率很差（22.0和22.0）。
Calixarenes 1 and their derivatives have attracted considerable attention over the past two decades. This attention can be attributed to their applications in areas as diverse as gas adsorption,[1] nanotubes,[2] catalysis,[3] DNA recognition [4] and fullerene chemistry.[5] Recently, many calixarene analogues have been developed in supramolecular chemistry, such as calixpyrroles,[6] thiacalixarenes,[7] and homooxacalixarenes.[8] In contrast to the vast literature about the meta-bridged cyclooligomers 1, very little is known about their para-bridged analogues 2, called pillar [n] arenes (Scheme 1). Recently, the first two members 2n (n= 5, R= OCH3, OH) of this series were reported.[9] They exhibit very interesting host–guest properties, but their preparation is rather tedious; the Lewis acid catalyzed condensation of 1, 4-dimethoxybenzene and paraformaldehyde furnishes a polymer, which contains some cyclic pentamer 25 (R= OCH3). Ether cleavage with BBr3 affords the pillar [5] arene with free hydroxy groups 25 (R= OH). The yields for the respective steps are poor (22.0 and