Chi Zhuomin, Zhou Yongchao, Liu Bingbing, Xu Xiaojing, Liu Xueyuan, Liang Yongmin
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University Lanzhou 730000 P. R. China
Chem Sci. 2024 Jul 23;15(33):13271-13278. doi: 10.1039/d4sc03067b. eCollection 2024 Aug 22.
The radical-mediated difunctionalization of 1,3-enynes facilitates rapid access to structurally diverse allenes and dienes. Whereas, owing to the existence of multiple active sites in conjugated 1,3-enynes, regulating selectivity in difunctionalized addition a single transition-metal-catalyzed radical tandem process remains elusive. Herein, we disclose an intriguing protocol of substrate-controlled nickel-catalyzed regiodivergent sulfonylarylation of 1,3-enynes with the assistance of sulfonyl chlorides and arylboronic acids. This valuable synthetic utility respectively delivers a series of highly functionalized and synthetically challenging allenyl sulfones and dienyl sulfones from fine-tuned 1,3-enynes by one step, which provides a facile approach for complex sulfone-containing drug molecules synthesis.
1,3-烯炔的自由基介导双官能团化反应有助于快速合成结构多样的丙二烯和二烯。然而，由于共轭1,3-烯炔中存在多个活性位点，在单一过渡金属催化的自由基串联过程中调控双官能团化加成反应的选择性仍然具有挑战性。在此，我们报道了一种有趣的方法，即在磺酰氯和芳基硼酸的辅助下，通过底物控制实现镍催化1,3-烯炔的区域发散性磺酰芳基化反应。这种有价值的合成方法可通过一步反应，从经过精细调控的1,3-烯炔分别制备出一系列高度官能团化且具有合成挑战性的烯丙基砜和二烯基砜，为合成含砜复杂药物分子提供了一种简便的方法。
