Department of Chemistry and Biochemistry, University of California─Los Angeles, Los Angeles, California 90095-1569, United States.
J Am Chem Soc. 2022 Aug 17;144(32):14828-14837. doi: 10.1021/jacs.2c05980. Epub 2022 Aug 4.
In this paper, we report the synthesis of alkyl-tethered alkynes through ozone-mediated and Fe-catalyzed dealkenylative alkynylation of unactivated alkenes in the presence of alkynyl sulfones. This one-pot reaction, which employs a combination of a catalytic Fe salt and l-ascorbic acid, proceeds under mild conditions with good efficiency, high stereoselectivity, and broad functional group compatibility. In contrast to our previous Fe-mediated reductive fragmentation of α-methoxyhydroperoxides, the Fe-catalyzed process was devised through a thorough kinetic analysis of the multiple competing radical (redox) pathways. We highlight the potential of this dealkenylative alkynylation through multiple post-synthetic transformations and late-stage diversifications of complex molecules, including natural products and pharmaceuticals.
在本文中，我们报告了通过臭氧介导和铁催化的未活化烯烃的脱烯基炔基化反应，在炔基砜存在下合成烷基键合炔烃。这种一锅反应采用催化铁盐和 l-抗坏血酸的组合，在温和的条件下进行，具有良好的效率、高立体选择性和广泛的官能团兼容性。与我们之前的 Fe 介导的α-甲氧基过氧化物的还原断裂反应不同，该铁催化过程是通过对多个竞争自由基（氧化还原）途径的详细动力学分析设计的。我们通过对复杂分子（包括天然产物和药物）的多种后合成转化和晚期多样化，突出了这种脱烯基炔基化反应的潜力。
