Highly Regio- and Stereoselective Heterogeneous Hydrosilylation of Terminal Alkynes over Cobalt-Metalated Porous Organic Polymer

Abstract

A cobalt/POL-PPh catalyzed ( E)-selective hydrosilylation of alkynes with PhSiH has been developed for the synthesis of ( E)-β-vinylsilanes with high regio- and stereoselectivity and wide functional group tolerance. It is the first report of using porous organic polymer as a recyclable regio- and stereoselective and efficient ligand in hydrosilylation reactions in which the polymer could be recycled numerous times in a continuous flow system without loss of activity and selectivity. The earth-abundant base-metal catalyst, coordinated by heterogeneous recyclable ligand, shows promise for industrial application.

Topotactic Synthesis of Phosphabenzene‐Functionalized Porous Organic Polymers: Efficient Ligands in CO2Conversion

“…However,o nly af ew examples of heterogeneous phosphine-based catalytic systems have been reported to date. [9][10][11][12][13] Fore xample,X iao et al reported as eries of diphosphine-ligand-containing porous frameworks obtained by polymerization of the vinyl-functionalized diphosphine monomers.T hese materials demonstrated superior catalytic performance in the hydroformylation of alkenes after treatment with Rh species. [12] Mesoporous poly(triphenylphosphine) with azo functionality (poly(PPh 3 )-azo) was synthesized by oxidative polymerization of aP ( m-NH 2 Ph) 3 monomer.…”

Topotactic Synthesis of Phosphabenzene‐Functionalized Porous Organic Polymers: Efficient Ligands in CO2Conversion

“…Nevertheless, heterogeneous phosphine‐based catalysts are more desirable for industrial applications because it is more convenient to recover and recycle them. However, only a few examples of heterogeneous phosphine‐based catalytic systems have been reported to date . For example, Xiao et al.…”

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

“…[19] Recently,o ur group reportedacobalt/POL-PPh 3 catalyzed (E)-selective hydrosilylation of alkynes with PhSiH 3 fort he synthesis of (E)-b-vinylsilanes with high regio-and stereo-selectivity and wide functional group tolerance (Figure3). [20] However,i nt his system,C obalt not catalytic activity with Ph 2 SiH 2 and internal alkynes will be reduced to alkenes or alkanes. Herein, we developahighly regioselectiveh ydrosilylation of internal and terminal alkynes with Ph 2 SiH 2 catalyzed by Co(acac) 2 /POL-Xantphos@10PPh 3 which recycled multiple times without loss of activity and selectivity ( Figure 3).…”