Shanghai Institute for Advanced Immunochemical Studies, ShanghaiTech University, 201210, Shanghai, China.
School of Life Science and Technology, ShanghaiTech University, 201210, Shanghai, China.
Angew Chem Int Ed Engl. 2020 Aug 3;59(32):13273-13280. doi: 10.1002/anie.202003595. Epub 2020 Apr 28.
Conventional direct C-H selenylation suffers from simple selenation with limited atom economy and complicated reaction system. In this work, we designed benzoselenazolone as a novel bifunctional selenide reagent for both off- and on-DNA C-H selenylation under rhodium(III) catalysis. We show that using benzoselenazolone allowed production of a series of selenylation products containing an adjacent aminoacyl group in a fast and efficient way, with high atom economy. The synthetic application of this method was demonstrated by taking advantage of the amide functionality as a nucleophile, directing group, and amide coupling partner. This work shows great potential in facilitating rapid construction of selenium-containing DNA-encoded chemical libraries (SeDELs), and lays the foundation for the development of selenium-containing drugs.
传统的直接 C-H 硒化反应存在简单硒化、原子经济性有限以及反应体系复杂等问题。在这项工作中，我们设计了苯并硒唑酮作为一种新型双功能硒试剂，在铑（III）催化下可实现 DNA 上的脱保护和保护 C-H 硒化。我们发现，使用苯并硒唑酮可以快速高效地得到一系列含有相邻氨基酰基的硒化产物，具有较高的原子经济性。该方法的合成应用通过利用酰胺官能团作为亲核试剂、导向基团和酰胺偶联伙伴得到了证明。这项工作为快速构建含硒 DNA 编码化学库（SeDELs）提供了巨大的潜力，并为含硒药物的开发奠定了基础。
