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Institute of Chemistry, Academia Sinica – Research

雙通過扭曲C=C雙鍵提升烯烴磷配體的供體強度卡本鉗形配位基及其對多金屬構型的配位行為

Increasing the Donor Strength of Alkenylphosphines by Twisting the C=C Double Bond

Angew. Chem. Int. Ed. 2025, 64, e202416764
Cheng-Han Yu, Yu-Wen Hsiao, Julian Löffler, Nicolas Kaiser, Bo-Hong Huang, Chao-Hsien Lee, Chen-Hsun Hung, Jiun-Shian Shen, Glenn P. A. Yap, Viktoria H. Gessner* Tiow-Gan Ong*

Increasing the Donor Strength of Alkenylphosphines by Twisting the C=C Double Bond

Electron-rich phosphines play a crucial role in transition metal-based homogeneous catalysis. While alkyl groups have traditionally been employed to increase the phosphine donor strength, recent studies have shown that zwitterionic functional groups such as phosphorus ylides can result in a further enhancement. Herein we report the concept of twisting a C=C double bond to introduce a zwitterionic substituent by the synthesis and application of N-heterocyclic olefin phosphines with a sulfonyl substituent (sNHOP). This sulfonyl group enables the twisting of the olefin moiety due to steric and electronic stabilization of the carbanionic center. The resulting zwitterionic structure leads to a significant increase of the donor strength of the sNHOP ligands compared to conventional NHOP systems with a planar N-heterocyclic olefin moiety. The potential of this new ligand platform for catalysis is demonstrated by its application in the gold-catalyzed hydroamination and cyclo-isomerization of alkynes. Here, the ligands outperform the original NHOP ligands suggesting favorable properties for future catalysis applications.

含豐富電子的磷配體在過渡金屬催化中發揮著關鍵作用。傳統上,烷基基團被用來增強磷配體的供體強度,但近期的研究發現,磷烯等雙性官能團能夠進一步提升這一強度。在此,我們提出了一種新思路,通過扭曲C=C雙鍵引入雙性取代基,進而合成並應用帶有磺醯基取代基的氮雜環烯烴磷配體(sNHOP)。磺醯基的引入通過立體和電子效應穩定了負電荷中心,從而導致烯烴部分的扭曲。相較于傳統的平面結構的NHOP配體,這種雙性結構顯著增強了sNHOP配體的供體強度。在「金」催化的烯烴加氨反應和環化異構化反應中,應用這種新型配體顯示了優異的催化性能,表明其在未來催化應用中的巨大潛力。