Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200438, China.
Zhejiang Key Laboratory of Alternative Technologies for Fine Chemical Process, Shaoxing University, Shaoxing, 312000, China.
Nat Commun. 2023 Mar 9;14(1):1301. doi: 10.1038/s41467-023-36704-9.
Transition-metal catalyzed asymmetric cyclization of 1,6-enynes has emerged as a powerful method for the construction of carbocycles and heterocycles. However, very rare examples worked under electrochemical conditions. We report herein a Co-catalyzed enantioselective intramolecular reductive coupling of enynes via electrochemistry using HO as hydride source. The products were obtained in good yields with high regio- and enantioselectivities. It represents the rare progress on the cobalt-catalyzed enantioselective transformation via electrochemistry with a general substrate scope. DFT studies explored the possible reaction pathways and revealed that the oxidative cyclization of enynes by LCo(I) is more favorable than oxidative addition of HO or other pathways.
过渡金属催化的 1,6-烯炔不对称环化反应已成为构建碳环和杂环的有力方法。然而，在电化学条件下进行的例子非常罕见。我们在此报告了一种通过电化学使用 HO 作为氢源的 Co 催化的对映选择性内分子还原偶联反应。该产物以良好的收率和高区域和对映选择性获得。这代表了在钴催化的对映选择性转化中通过电化学进行的罕见进展，具有广泛的底物范围。DFT 研究探讨了可能的反应途径，并表明 LCo(I) 对烯炔的氧化环化比 HO 或其他途径的氧化加成更有利。
