Huang Xi, Li Juan, Li Xiang, Wang Jiayi, Peng Yanqing, Song Gonghua
Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology Shanghai 200237 PR China
RSC Adv. 2019 Aug 22;9(45):26419-26424. doi: 10.1039/c9ra05708k. eCollection 2019 Aug 19.
A novel, efficient, catalyst-free and product-controllable strategy has been developed for the chemoselective α-sulfenylation/β-thiolation of α,β-unsaturated carbonyl compounds. An aromatic sulfur group could be chemoselectively introduced at α- or β-position of carbonyls with different sulfur reagents under slightly changed reaction conditions. A series of desired products were obtained in moderate to excellent yields. Mechanistic studies revealed that Bpin played the key role in activating the transformation towards the β-thiolation of α,β-unsaturated carbonyl compounds. This transition-metal-catalyst-free method provides a convenient and efficient tool for the highly chemoselective preparation of α-thiolation or β-sulfenylation products of α,β-unsaturated carbonyl compounds.
已开发出一种新颖、高效、无催化剂且产物可控的策略，用于α,β-不饱和羰基化合物的化学选择性α-硫醚化/β-硫醇化反应。在略有变化的反应条件下，使用不同的硫试剂可将芳基硫基化学选择性地引入羰基的α-或β-位。以中等到优异的产率获得了一系列所需产物。机理研究表明，频哪醇硼酸酯（Bpin）在促进α,β-不饱和羰基化合物向β-硫醇化的转化中起关键作用。这种无过渡金属催化剂的方法为高效化学选择性制备α,β-不饱和羰基化合物的α-硫醇化或β-硫醚化产物提供了一种便捷有效的工具。
