Tandem Reactivity of a Self-Assembled Cage Catalyst with Endohedral Acid Groups
Tandem Reactivity of a Self-Assembled Cage Catalyst with Endohedral Acid Groups
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DOI：
10.1021/jacs.8b03984
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发表时间：
2018-07-04
影响因子：
15
通讯作者：
Hooley, Richard J.
中科院分区：
文献类型：
--
作者：
Holloway, Lauren R.;Bogie, Paul M.;Hooley, Richard J.
含羧酸的配体自组装成Fe 4L 6亚氨基吡啶笼允许酸基团的内面定位，同时保持稳健的笼结构。笼是一种有效的超分子催化剂，提供高达1000倍的缩醛溶剂分解速率增强。这种增强的反应性允许串联脱保护/笼与笼的相互转化，这是用其他酸催化剂不能实现的。速率增强和反应功能的螯合的组合赋予该过程活性和选择性，模拟酶的行为。
Self-assembly of a carboxylic acid-containing ligand into an Fe4L6 iminopyridine cage allows endohedral positioning of the acid groups while maintaining a robust cage structure. The cage is an effective supramolecular catalyst, providing up to 1000-fold rate enhancement of acetal solvolysis. This enhanced reactivity allows a tandem deprotection/cage-to-cage interconversion that cannot be achieved with other acid catalysts. The combination of rate enhancements and sequestration of the reactive function confers both activity and selectivity on the process, mimicking enzymatic behavior.