Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.
Angew Chem Int Ed Engl. 2022 Sep 19;61(38):e202210632. doi: 10.1002/anie.202210632. Epub 2022 Aug 17.
A simplified and appealing strategy via a chiral catalyst to facilitate the electrochemical process and provide asymmetric induction of radical reactions is particularly desirable and would have potential applications in electrosynthesis, organic chemistry, and drug discovery. Here, we introduced a novel electrolytic system that diverts the standard ionic reactivity to new catalytic functions, enabling mechanistically distinct single-electron transfer-based enantioselective routes to exhibit a brand-new pattern of reactivity-electricity-driven asymmetric catalysis as a privileged chiral platform for enantioselective radical allylation. The nickel-catalyzed activation of nucleophiles triggered a single-electron transfer process to provide a chiral catalyst-bound radical cation intermediate, which could be applied as an alternative strategy for the development of stereocontrolled radical reactions.
通过手性催化剂简化并吸引一种策略,以促进电化学过程并提供自由基反应的不对称诱导,这是特别可取的,并且可能在电合成、有机化学和药物发现中有潜在的应用。在这里,我们引入了一种新颖的电解系统,将标准的离子反应转化为新的催化功能,使基于机制上不同的单电子转移的对映选择性途径表现出一种全新的反应模式——电驱动不对称催化,作为手性平台用于对映选择性自由基烯丙基化。亲核试剂的镍催化活化引发了单电子转移过程,提供了手性催化剂结合的自由基阳离子中间体,这可以作为发展立体控制的自由基反应的替代策略。