Xantphos Doped POPs‐PPh3 as Heterogeneous Ligand for Cobalt‐Catalyzed Highly Regio‐ and Stereoselective Hydrosilylation of Alkynes

A Co(acac)₂/POL‐Xantphos@10PPh₃‐catalyzed hydrosilylation of unsymmetrical internal alkynes with Ph₂SiH₂ has been developed for the synthesis of highly selective syn‐α‐vinylsilane products. Furthermore, terminal alkynes were also used and gave the products with excellent regioselectivity and a wide functional group tolerance. Because this porous organic polymer combines the selectivity and activity merits of Xantphos with the stability advantage derived from the high concentration of PPh₃, the Co(acac)₂/POL‐Xantphos@10PPh₃ can be recycled multiple times without loss of activity and selectivity. This heterogeneous catalyst is expected to find promising applications in industrial synthesis.