Wu Zhao-Juan, Li Ziyang, Ren Yue, Meng Ling-Guo
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Anhui Provincial Key Laboratory of Synthetic Chemistry and Applications, Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, People's Republic of China.
Org Lett. 2025 Jan 10;27(1):115-120. doi: 10.1021/acs.orglett.4c04015. Epub 2024 Dec 23.
Recent advances in dual catalysis involving biomimetic conversion strategies that utilize radical ligand transfer (RLT) often rely on large doses of precious metal additives. The role of these additives within the mechanism remains ambiguous, leading to complex reaction conditions, uncertain pathways, and increased costs. These challenges complicate the study of the reaction process and are accompanied by potential safety risks. To address these issues, azide salt was used as an alternative to TMSN. This replacement not only avoids the drawbacks associated with almost parallel research on alkene azidodifluoroalkylation but also eliminates the need for ligands. Comparative analysis indicates that existing biomimetic synergistic catalysis strategies require AgCO additives to enhance selectivity in alkene difunctionalization reactions, highlighting the superior simplicity, environmental friendliness, and operational ease of our developed synergistic catalysis strategy. Furthermore, under the guidance of our proposed mechanism, an alkene azidosulfonation was designed, validating the innovative and practical applicability of our synergistic catalysis approach.
涉及利用自由基配体转移(RLT)的仿生转化策略的双催化领域的最新进展通常依赖于大剂量的贵金属添加剂。这些添加剂在反应机理中的作用仍不明确,导致反应条件复杂、反应途径不确定且成本增加。这些挑战使反应过程的研究变得复杂,并伴随着潜在的安全风险。为了解决这些问题,叠氮盐被用作三甲基硅基叠氮化物(TMSN)的替代品。这种替代不仅避免了与烯烃叠氮二氟烷基化几乎平行研究相关的缺点,还消除了对配体的需求。对比分析表明,现有的仿生协同催化策略需要碳酸银添加剂来提高烯烃双官能化反应的选择性,凸显了我们所开发的协同催化策略具有更高的简便性、环境友好性和操作便利性。此外,在我们提出的机理指导下,设计了烯烃叠氮磺化反应,验证了我们的协同催化方法的创新性和实际适用性。