Regio- and Stereoselective Synthesis of Multisubstituted Olefins and Conjugate Dienes by Using α-Oxo Ketene Dithioacetals as the Building Blocks

An efficient palladium(0)-catalyzed, Cu(I)-mediated synthetic route to trisubstituted olefins and conjugate dienes has been developed via oxo directing Liebeskind–Srogl cross-coupling reactions of gem-dihaloolefin-type α-oxo ketene dithioacetals with aryl and alkenylboronic acids. The synthetic protocol has demonstrated rare examples of transition-metal-promoted transformations of ketene dithioacetals, providing a novel route to highly functionalized conjugate dienes.

本研究开发了一条高效的钯(0)催化、铜(I)介导的合成路线，可用于制备三取代烯烃与共轭二烯烃；该路线通过偕二卤烯烃型α-氧代烯酮二硫缩醛（gem-dihaloolefin-type α-oxo ketene dithioacetals）与芳基、烯基硼酸的含氧导向Liebeskind–Srogl交叉偶联反应（Liebeskind–Srogl cross-coupling reactions）实现。该合成策略已展现出过渡金属促进烯酮二硫缩醛（ketene dithioacetals）转化的罕见案例，为高度官能化的共轭二烯烃提供了全新的合成路径。