化学
分子间力
氢化物
分子内力
反键分子轨道
单独一对
反应性(心理学)
溶剂
光化学
计算化学
有机化学
分子
氢
医学
物理
替代医学
病理
量子力学
原子轨道
电子
作者
Shaokun Cai,Hong Tang,Bo Li,Yingbo Shao,Danqi Zhang,Hanliang Zheng,Tianjiao Qiao,Xin Chu,Gang He,Xiao‐Song Xue,Gong Chen
摘要
The ability of alkylamines to spontaneously liberate hydride ions is typically restrained, except under specific intramolecular reaction settings. Herein, we demonstrate that this reactivity can be unlocked through simple treatment with formaldehyde in hexafluoroisopropanol (HFIP) solvent, thereby enabling various intermolecular hydride transfer reactions of alkylamines under mild conditions. Besides transformations of small molecules, these reactions enable unique late-stage modification of complex peptides. Mechanistic investigations uncover that the key to these intermolecular hydride transfer processes lies in the accommodating conformation of solvent-mediated macrocyclic transition states, where the aggregates of HFIP molecules act as dexterous proton shuttles. Importantly, negative hyperconjugation between the lone electron pair of nitrogen and the antibonding orbital of amine's α C–H bond plays a critical role in the C–H activation, promoting its hydride liberation.
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