Kuhlmann Jan H, Dickoff Jan H, Mancheño Olga García
Organic Chemistry Institute, University of Münster, Corrensstraße 36, 48149, Münster, Germany.
Chemistry. 2023 Feb 24;29(12):e202203347. doi: 10.1002/chem.202203347. Epub 2023 Jan 20.
A straightforward, visible-light triggered desilylation of arylsilanes by thiyl radicals is presented. Silyl groups are often used to block a reactive position in multi-step organic synthesis, for which a mild cleavage at a late-stage will provide new possibilities and disconnection routes by C -Si cleavage/deprotection. In this work, commercially available and cheap disulfides are employed for the first time in this type of C(sp )-Si bond cleavage reactions. Thus, upon irradiation with visible-light, homolytic cleavage of the disulfide give rise to the corresponding thiyl radical that allows for a radical chain mechanism. This methodology represents a mild, fast and simple approach suitable for a broad variety of simply substituted arylsilanes. Moreover, the procedure could be easily extended to natural products and therapeutic derivatives, showing its robustness and synthetic application potential.
本文介绍了一种简单的、可见光引发的硫自由基介导的芳基硅烷去硅基化反应。硅烷基通常用于多步有机合成中阻断反应位点，后期温和的裂解将通过C-Si裂解/脱保护提供新的可能性和切断路线。在这项工作中，首次在这类C(sp)-Si键裂解反应中使用市售且廉价的二硫化物。因此，在可见光照射下，二硫化物的均裂产生相应的硫自由基，从而引发自由基链反应机理。该方法是一种温和、快速且简单的方法，适用于多种简单取代的芳基硅烷。此外，该方法可以很容易地扩展到天然产物和治疗性衍生物，显示出其稳健性和合成应用潜力。
