A Co(acac) /POL-Xantphos@10PPh -catalyzed hydrosilylation of unsymmetrical internal alkynes with Ph SiH 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 PPh , the Co(acac) /POL-Xantphos@10PPh can be recycled multiple times without loss of activity and selectivity. This heterogeneous catalyst is expected to find promising applications in industrial synthesis.
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