A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions
A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions
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DOI：
10.1016/j.chempr.2022.11.006
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发表时间：
2023-03-09
期刊：
影响因子：
23.5
通讯作者：
Lu, Erli
中科院分区：
文献类型：
--
作者：
Davison, Nathan;Quirk, James A.;Lu, Erli
在这项工作中，我们报道了一个室温稳定的电极（RoSE）试剂，即K+(LiHMDS)e- (1) （HMDS: 1,1,1,3,3,3-六甲基二二氮化脲），在20 mmol的规模下，由可获得的原料（金属钾和LiHMDS）通过机械化学球磨合成。尽管它的无定形性质，阴离子电子在1中的存在，一个关键的诊断标准的电子，是由实验和计算研究证实。因此，根据定义，1是一个电子。利用其阴离子电子，electride试剂1表现出多种反应性，包括(1)介导苯和吡啶的C-H活化和C-C偶联，(2)介导无溶剂桦木还原。这项工作证明了一种室温稳定的电子化合物的简单机械化学合成的概念，并将电子化合物1作为一种多功能的重试剂引入合成化学界。
In this work, we report the synthesis of a room-temperature-stable electride (RoSE) reagent, namely K+(LiHMDS)e- (1) (HMDS: 1,1,1,3,3,3-hexamethyldisilazide), from accessible starting mate-rials (potassium metal and LiHMDS) via mechanochemical ball mill-ing at 20 mmol scale. Despite its amorphous nature, the presence of anionic electrons in 1, key diagnostic criteria for an electride, was confirmed by both experimental and computational studies. Therefore, by definition, 1 is an electride. Utilizing its anionic elec-trons, electride reagent 1 exhibited a versatile reactivity profile that includes (1) mediation of C-H activation and C-C coupling of benzene and pyridine and (2) mediation of solvent-free Birch reduc-tion. This work proves the concept of facile mechanochemical syn-thesis of a room-temperature-stable electride, and it introduces electride 1 to the synthetic chemistry community as a versatile re-agent.