Magnetic Nanoparticles as an Orthogonal Support of Polymer Resins:  Applications to Solid-Phase Suzuki Cross-Coupling Reactions

Abstract

[reaction: see text] Most of the reactants immobilized on conventional solid-phase resins are buried inside the interiors of lightly cross-linked polystyrene beads. An orthogonal support of solid-phase resins needs to be small enough to penetrate the interpolymeric chain spaces of a swollen resin to reach reaction sites. In this paper, we report the use of magnetic nanoparticles ( approximately 4 nm) as an orthogonal matrix to assist solid-phase reactions. A magnetic nanoparticle-supported homogeneous Pd catalyst was employed for promoting the Suzuki cross-coupling of an aryl halide on resins and an excessive arylboronic acid in solution. The workup separating three components (the catalyst, product, and remaining arylborate) is a chromatography-free process. The Pd catalyst was magnetically isolated and recycled from the reaction mixture by applying an external magnetic field. Then, a filtration process was followed to recover the excess borate reagent from the resins/product. Our work here presents the first example of an orthogonal matrix of solid-phase resins and shows the promise of employing nanomaterials in organic synthesis.