A supramolecular approach to an allosteric catalyst
A supramolecular approach to an allosteric catalyst
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DOI：
10.1021/ja035621h
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发表时间：
2003-09-03
影响因子：
15
通讯作者：
Rheingold, AL
中科院分区：
文献类型：
--
作者：
Gianneschi, NC;Bertin, PA;Rheingold, AL
设计和合成了一种新的，超分子变构催化剂系统，组装通过弱连接的方法，提出。该催化剂含有两个结构Rh（I）中心的硫醚和膦丰富的半不稳定口袋，和两个功能的铬（III）中心结合在基于Salen的部分。的超分子催化剂的催化性能进行比较的铬（III）-salen单体类似物的上下文中的氧化环己烯的不对称开环的TMSN 3。变构控制是通过在远端位点发生的反应提供的，该反应打开大环空腔并促进催化反应。动力学数据显示，在打开催化剂的灵活的大环腔和增强的选择性和反应性相对于单体的Cr（III）-salen类似物的显着的速率增加。该工作为构建非生物变构催化剂提供了一种新的途径。
The design and synthesis of a novel, supramolecular allosteric catalyst system, assembled via the weak-link approach, is presented. The catalyst contains two structural Rh(I) centers in thioether- and phosphine-rich hemilabile pockets, and two functional Cr(III) centers bound within salen-based moieties. The catalytic properties of the supramolecular catalyst are compared to those of a Cr(III)-salen monomeric analogue in the context of the asymmetric ring opening of cyclohexene oxide by TMSN3. Allosteric control is afforded via reactions that occur at distal sites which open the macrocyclic cavity and facilitate the catalytic reaction. Kinetic data show a significant rate increase upon opening of the catalyst's flexible macrocyclic cavity and enhanced selectivity and reactivity with respect to the monomeric Cr(III)-salen analogue. The work presented represents a new approach to the construction of abiotic allosteric catalysts.