Department of Chemistry , University of California-Riverside , Riverside , California 92521 , United States.
J Am Chem Soc. 2018 Jul 5;140(26):8078-8081. doi: 10.1021/jacs.8b03984. Epub 2018 Jun 20.
Self-assembly of a carboxylic acid-containing ligand into an FeL 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.
羧酸配体的自组装形成了一个 FeL 亚氨基吡啶笼，允许酸基团在内腔中定位，同时保持坚固的笼状结构。该笼是一种有效的超分子催化剂，可使缩醛的溶剂解反应速率提高高达 1000 倍。这种增强的反应性使得可以进行串联的脱保护/笼到笼的转化，而其他酸催化剂则无法实现。反应性官能团的速率增强和隔离赋予了该过程活性和选择性，模拟了酶的行为。
