Synthesis of a carbene transfer organometallic polymer and application to forming a recyclable heterogeneous catalyst for the Suzuki reactions of aryl chlorides

Abstract

An efficient and versatile synthetic approach to NHC-based organometallic polymers has been developed by a simple three-step synthesis. A novel brush polymer having imidazolium salt side chains (P2) was firstly synthesized through postpolymerization modification of P1, which permits access to Ag(I)–NHC-based side chain polymer (P3) at room temperature in high yield. P3 was applied as a carbene transfer agent to form a Pd–NHC-containing polymer (P4) by the transmetallation reaction of Ag(I)–NHCs in the side chains. Inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis indicated that 77% of Ag(I)–NHCs in the side chains of P3 were transmetallated. The resulting Pd–NHC-containing polymer (P4) showed high catalytic activity and reusability in the Suzuki reactions of aryl chlorides and aryl boronic acids. This novel Pd–NHC-containing polymeric catalyst was used five times and still remained active giving the desired biaryl products in 70% yield in the fifth run of the cross-coupling reaction of deactivated 4-chloroanisole with phenylboronic acid.