当前位置: X-MOL 学术Chem. Sci. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Nickel/photoredox-catalyzed three-component silylacylation of acrylates via chlorine photoelimination
Chemical Science ( IF 8.4 ) Pub Date : 2024-04-24 , DOI: 10.1039/d4sc02164a
Yejin Koo 1, 2 , Sungwoo Hong 1, 2
Affiliation  

The extensive utility of organosilicon compounds across a wide range of disciplines has sparked significant interest in their efficient synthesis. Although catalytic 1,2-silyldifunctionalization of alkenes provides a promising method for the assembly of intricate organosilicon frameworks with atom and step economy, its advancement is hindered by the requirement of an external hydrogen atom transfer (HAT) agent in photoredox catalysis. Herein, we disclose an efficient three-component silylacylation of α,β-unsaturated carbonyl compounds, leveraging a synergistic nickel/photoredox catalysis with various hydrosilanes and aroyl chlorides. This method enables the direct conversion of acrylates into valuable building blocks that contain both carbonyl and silicon functionalities through a single, redox-neutral process. Key to this reaction is the precise activation of the Si–H bond, achieved through chlorine radical-induced HAT, enabled by the photoelimination of a Ni–Cl bond. Acyl chlorides serve a dual role, functioning as both acylating agents and chloride donors. Our methodology is distinguished by its mild conditions and extensive substrate adaptability, significantly enhancing the late-stage functionalization of pharmaceuticals.

中文翻译:

镍/光氧化还原催化的丙烯酸酯通过氯光消除的三组分甲硅烷基酰化

有机硅化合物在多个学科中的广泛应用引起了人们对其高效合成的浓厚兴趣。尽管烯烃的催化 1,2-甲硅烷基双官能化为组装具有原子和步骤经济性的复杂有机硅框架提供了一种有前途的方法,但其进展受到光氧化还原催化中外部氢原子转移(HAT)试剂的需求的阻碍。在此,我们公开了α,β-不饱和羰基化合物的有效三组分甲硅烷基酰化,利用镍/光氧化还原催化与各种氢硅烷和芳酰氯的协同作用。该方法能够通过单一的氧化还原中性过程将丙烯酸酯直接转化为含有羰基和硅官能团的有价值的结构单元。该反应的关键是 Si-H 键的精确激活,这是通过氯自由基诱导的 HAT 实现的,并通过 Ni-Cl 键的光消除实现。酰氯具有双重作用,既充当酰化剂又充当氯供体。我们的方法以其温和的条件和广泛的底物适应性而著称,显着增强了药物的后期功能化。
更新日期:2024-04-29
down
wechat
bug