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.