Institut für Chemie , Technische Universität Berlin , Strasse des 17. Juni 115 , 10623 Berlin , Germany.
J Am Chem Soc. 2019 Jan 16;141(2):1135-1140. doi: 10.1021/jacs.8b12318. Epub 2018 Dec 28.
The design and a gram-scale synthesis of a bench-stable cyclohexa-1,4-diene-based surrogate of gaseous hydrogen iodide are described. By initiation with a moderately strong Brønsted acid, hydrogen iodide is transferred from the surrogate onto C-C multiple bonds such as alkynes and allenes without the involvement of free hydrogen iodide. The surrogate fragments into toluene and ethylene, easy-to-remove volatile waste. This hydroiodination reaction avoids precarious handling of hydrogen iodide or hydroiodic acid. By this, a broad range of previously unknown or difficult-to-prepare vinyl iodides can be accessed in stereocontrolled fashion.
本文描述了一种环己-1,4-二烯基气体碘化氢替代物的设计和克级合成。通过与中等强度的布朗斯特酸引发反应，碘化氢从替代物转移到炔烃和丙二烯等 C-C 多重键上，而无需游离碘化氢的参与。替代物分解为甲苯和乙烯，这是易于去除的挥发性废物。这种碘化氢反应避免了碘化氢或氢碘酸的危险处理。通过这种方法，可以以立体控制的方式获得以前未知或难以制备的各种顺式或反式乙烯基碘化物。
