Du Yi-Ming, Chen Xiao-Yi, Li Yulong, Koh Ming Joo, Shu Wei
Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Shenzhen Grubbs Institute, Guangming Advanced Research Institute, Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong, PR China.
College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong, Sichuan, PR China.
Nat Commun. 2025 May 5;16(1):4163. doi: 10.1038/s41467-025-57967-4.
Enantioenriched α-arylated dialkyl ketones with acidic proton are ubiquitous subunits in valuable target organic molecules and serve as versatile synthetic precursors for other value-added chiral blocks. Herein, a distinct synthetic strategy of enantioenriched α-arylated dialkyl ketones enabled by nickel-catalyzed iterative cross-hydrocarbonylation of two alkenes has been developed, representing a reaction mode for the direct synthesis of asymmetric α-arylated dialkyl ketones. One aliphatic alkene and one styrene are creatively used as surrogates of two different alkyl precursors. Two different alkenes are sewed together by a "carbonyl glue" with exclusive alkene sorting. This straightforward and gas-free protocol transforms a diverse array of styrene and unactivated alkenes into highly valuable α-arylated dialkyl ketones with high levels of enantioselectivity, allowing for the construction of enantioenriched unsymmetric dialkyl ketones from only alkenes. This process is also applicable to late-stage functionalization of complex molecules.
具有酸性质子的对映体富集的α-芳基二烷基酮是有价值的目标有机分子中普遍存在的亚基，并且作为其他增值手性砌块的通用合成前体。在此，已经开发了一种独特的合成对映体富集的α-芳基二烷基酮的策略，该策略通过镍催化的两种烯烃的迭代交叉氢羰基化反应实现，代表了一种直接合成不对称α-芳基二烷基酮的反应模式。一种脂肪族烯烃和一种苯乙烯被创造性地用作两种不同烷基前体的替代物。两种不同的烯烃通过具有排他性烯烃分类的“羰基胶水”缝合在一起。这种直接且无气体的方法将各种苯乙烯和未活化的烯烃转化为具有高对映选择性的高价值α-芳基二烷基酮，从而能够仅从烯烃构建对映体富集的不对称二烷基酮。该过程也适用于复杂分子的后期官能团化。
