Process Research and Development, Merck & Co., Inc., Rahway, NJ 07065, USA.
Analytical Research and Development, Merck & Co., Inc., Rahway, NJ 07065, USA.
Angew Chem Int Ed Engl. 2023 May 2;62(19):e202217623. doi: 10.1002/anie.202217623. Epub 2023 Mar 31.
The development and mechanistic investigation of a nickel-catalyzed sulfonylation of aryl bromides is disclosed. The reaction proceeds in good yields for a variety of substrates and utilizes an inexpensive, stench-free, inorganic sulfur salt (K S O ) as a uniquely effective SO surrogate. The active oxidative addition complex was synthesized, isolated, and fully characterized by a combination of NMR spectroscopy and X-ray crystallography analysis. The use of the isolated oxidative addition complex in both stoichiometric and catalytic reactions revealed that SO insertion occurs via dissolved SO , likely released upon thermal decomposition of K S O . Key to the success of the reaction is the role of K S O as a reservoir of SO that is slowly released, thus preventing catalyst poisoning.
公开了一种镍催化的芳基溴化物磺酰化反应的发展和机理研究。该反应在各种底物上都能以良好的收率进行，并且使用一种廉价、无恶臭的无机硫盐（K 2 S 2 O 8 ）作为独特有效的 SO 替代物。通过 NMR 光谱和 X 射线晶体学分析的组合，合成、分离并完全表征了活性氧化加成配合物。在计量和催化反应中使用分离的氧化加成配合物表明，SO 插入是通过溶解的 SO 发生的，可能是 K 2 S 2 O 8 热分解时释放出来的。反应成功的关键是 K 2 S 2 O 8 作为 SO 缓慢释放的储库的作用，从而防止催化剂中毒。
