Department of Chemistry, Johns Hopkins University, 3400 N. Charles St., Baltimore, MD 21218, USA.
Angew Chem Int Ed Engl. 2022 Aug 22;61(34):e202207966. doi: 10.1002/anie.202207966. Epub 2022 Jul 13.
The putative interaction of a C-F bond with an amide carbonyl has been an intriguing topic of interest in this century for reasons spanning basic physical organic chemistry to biochemistry. However, to date, there exist no examples of a close, well-defined interaction in which its unique aspects can be identified and exploited. Herein, we finally present an engineered system possessing an exceptionally tight C-F-amide interaction, allowing us to obtain spectroscopic, crystallographic, and kinetic details of a distinctive, biochemically relevant chemical system for the first time. In turn, we also explore Lewis acid coordination, C-F bond promotion of amide isomerization, enantiomerization, and ion protonation processes.
本世纪以来，C-F 键与酰胺羰基之间的假定相互作用一直是一个有趣的研究课题，其原因涉及基础物理有机化学到生物化学等多个领域。然而，迄今为止，还没有发现任何接近、明确的相互作用的例子，其中可以确定和利用其独特的方面。在此，我们终于提出了一个具有非常紧密的 C-F-酰胺相互作用的工程体系，使我们首次获得了一个独特的、具有生物相关性的化学体系的光谱、晶体学和动力学细节。反过来，我们还探索了路易斯酸配位、C-F 键促进酰胺异构化、对映体异构化和离子质子化过程。
