Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua 321004, China.
Org Biomol Chem. 2013 Apr 7;11(13):2175-85. doi: 10.1039/c3ob27307e.
An operationally simple and practical protocol for the synthesis of (E)-α-halo vinyl sulfides has been achieved via a highly regio- and stereoselective hydrohalogenation of alkynyl thioethers using lithium halides in HOAc or propionic acid at room temperature. It permits the formation of (E)-α-chloro and (E)-α-bromo vinyl sulfides in satisfactory yields with good to excellent stereoselectivities. Moreover, this work results in a new method for the assembly of stereodefined (E)- or (Z)-trisubstituted alkenes featuring the first coupling of the C-X bond of (E)-α-halo vinyl sulfides followed by a subsequent Ni-catalyzed coupling of the C-S bond with Grignard reagents.
通过在 HOAc 或丙酸中使用卤化锂，在室温下对炔基硫醚进行高区域和立体选择性的氢卤化反应，实现了（E）-α-卤代乙烯基硫醚的合成的操作简单实用的方案。它允许以令人满意的产率和良好至优异的立体选择性形成（E）-α-氯和（E）-α-溴乙烯基硫醚。此外，这项工作导致了一种新的方法，用于立体定义的（E）-或（Z）-三取代烯烃的组装，其特征在于首先偶联（E）-α-卤代乙烯基硫醚的 C-X 键，然后随后用镍催化的 C-S 键与格氏试剂偶联。
