Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University , 3663 North Zhongshan Road, Shanghai 200062, People's Republic of China.
Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL , 46, Allée d'Italie, F-69364 Lyon, France.
Chem Rev. 2017 Mar 22;117(6):4900-4942. doi: 10.1021/acs.chemrev.6b00847. Epub 2017 Mar 9.
In the wide area of host-guest chemistry, hemicryptophanes, combining a cyclotribenzylene (or cyclotriveratrylene CTV) unit with another different C-symmetrical moiety, appears as a recent family of molecular cages. The synthesis and recognition properties of the first hemicryptophane were reported in 1982 by Collet and Lehn, but the very little attention received by this class of host compounds in the 20 years following this first promising result can account for their apparent novelty. Indeed, in the last 10 years hemicryptophanes have aroused growing interest, and new aspects have been developed. Thanks to the rigid shaping unit of the north part (CTV) and also the variable and easily functionalized south moiety, hemicryptophanes are revealed to be inherently chiral ditopic host compounds, able to encapsulate various guests, including charged and neutral species. They also enter the field of stimuli-responsive supramolecular systems exhibiting controlled functions. Moreover, endohedral functionalization of their inner cavity leads to supramolecular catalysts. The confinement of the catalytic center affords nanoreactors with improved catalytic activities or selectivities when compared to model systems without a cavity. The current trend shows that reactions in the confined space of synthetic hosts, mimicking enzyme behavior, will expand rapidly in the near future.
在主体客体化学的广阔领域中，半穴状化合物是一类新型的分子笼，它将环三苯并[2,1-b:2',1'-f][1,3,5]三嗪（或环三藜芦基 CTV）单元与另一个不同的 C 对称部分结合在一起。1982 年，Collet 和 Lehn 首次报道了首例半穴状化合物的合成和识别特性，但在这一有前景的结果之后的 20 年里，这类主体化合物受到的关注甚少，这可以解释它们明显的新颖性。事实上，在过去的 10 年里，半穴状化合物引起了越来越多的兴趣，并且出现了新的发展。由于北部（CTV）部分的刚性塑造单元和可变且易于功能化的南部部分，半穴状化合物被揭示为固有的手性双位点主体化合物，能够包封各种客体，包括带电和中性物质。它们还进入了具有可控功能的刺激响应超分子体系领域。此外，其内部空腔的内包功能化导致超分子催化剂。与没有空腔的模型体系相比，催化中心的限制为纳米反应器提供了改进的催化活性或选择性。目前的趋势表明，在合成主体的受限空间内进行反应，模拟酶的行为，将在不久的将来迅速扩展。
