Zhang Zeyu, Han Zongchang, Shang Yuhao, Hu Han-Shi, Li Jun, Xi Chanjuan
Department of Chemistry, MOE Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Tsinghua University, Beijing, 100084, P. R. China.
Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, Beijing, 100084, P. R. China.
Adv Sci (Weinh). 2025 Aug;12(31):e07490. doi: 10.1002/advs.202507490. Epub 2025 Jun 9.
An efficient photoinduced and metal-free method for direct α-C-H monoalkylation of alcohols utilizing the CO-DBU-system as a hydrogen bond acceptor (HBA) catalyst in the presence of water (HO) is reported. This protocol allows for selective functionalization of alcohols with a broad substrate scope, demonstrating yields up to 88% in 36 examples. Systematic computational analysis using DFT calculations reveals insights into the mechanism by identifying the key intermediates assembled via intermolecular hydrogen bond between DBU-CO adduct and alcohol. This strategy opens new avenues for efficient alkylation of ordinary alcohols, offering an environmentally friendly approach to complex molecular synthesis.
报道了一种高效的光诱导且无金属的方法，用于醇的直接α-C-H单烷基化反应，该反应在水（HO）存在下利用CO-DBU体系作为氢键受体（HBA）催化剂。此方案允许对具有广泛底物范围的醇进行选择性官能化，在36个实例中展示了高达88%的产率。使用DFT计算进行的系统计算分析通过识别经由DBU-CO加合物与醇之间的分子间氢键组装的关键中间体，揭示了反应机理的见解。该策略为普通醇的高效烷基化开辟了新途径，为复杂分子合成提供了一种环境友好的方法。
