Institut des Sciences Chimiques de Rennes-UMR 6226, CNRS-Université de Rennes 1, Campus de Beaulieu 35042 Rennes (France).
Angew Chem Int Ed Engl. 2015 Oct 5;54(41):12112-5. doi: 10.1002/anie.201505144. Epub 2015 Aug 24.
An unprecedented ruthenium-catalyzed direct and selective alkyne hydrochlorination is reported and leads to vinylchlorides in excellent yields with atom economy. The reaction proceeds at room temperature from terminal alkynes and provides a variety of chloroalkenes. Only the regioisomer resulting from the formal Markovnikov addition is selectively formed. Mechanistic studies show the stereoselective syn addition of HCl to alkynes at room temperature and suggest a chloro hydrido Ru(IV) species as a key intermediate of the reaction.
报道了首例钌催化的炔烃的直接和选择性氯化反应，该反应以原子经济性得到了高产率的氯代乙烯。反应在室温下从末端炔烃进行，提供了多种氯代烯烃。仅形成了由形式马氏加成得到的区域异构体。机理研究表明，HCl 在室温下立体选择性地syn 加成到炔烃上，并提出了一个氯氢合钌（IV）物种作为反应的关键中间体。
