College of Chemistry, Beijing Normal University, Beijing, 100875, China.
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Angew Chem Int Ed Engl. 2022 Sep 26;61(39):e202209044. doi: 10.1002/anie.202209044. Epub 2022 Aug 19.
The use of alkylthio electrophiles in synthesis has remained elusive because of the lack of a suitable reagent that is practical and of excellent enantioselectivity and appropriate reactivity. In this work we introduce a novel alkylthio reagent based on the 2-mercapto-5-methyl-1,3,4-thiadiazole (MMTD) fragment for direct alkylsulfenylation of ketones and aldehydes. It can be readily prepared by the oxidative coupling between thiadiazole and other alkylthio reagents and be combined with chiral primary aminocatalysis. This protocol provides facile access to diverse α-alkylthio quaternary carbon centers with good stereoselectivities.
由于缺乏实用、对映选择性优异且反应性适中的合适试剂，烷基硫亲电试剂在合成中的应用一直难以实现。在这项工作中，我们引入了一种基于 2-巯基-5-甲基-1,3,4-噻二唑 (MMTD) 片段的新型烷基硫试剂，用于酮和醛的直接烷基磺酰化反应。它可以通过噻二唑与其他烷基硫试剂之间的氧化偶联轻松制备，并与手性伯氨基催化相结合。该方案为各种具有良好立体选择性的α-烷基硫季碳中心的构建提供了便捷途径。
