Boron insertion into alkyl ether bonds via zinc/nickel tandem catalysis

Mild methods to cleave the carbon-oxygen (C-O) bond in alkyl ethers could simplify chemical syntheses through the elaboration of these robust, readily available precursors. Here we report that dibromoboranes react with alkyl ethers in the presence of a nickel catalyst and zinc reductant to insert boron into the C-O bond. Subsequent reactivity can effect oxygen-to-nitrogen substitution or one-carbon homologation of cyclic ethers and more broadly streamline preparation of bioactive compounds. Mechanistic studies reveal a cleavage-then-rebound pathway via zinc/nickel tandem catalysis.

Automated summary

Mild methods for cleaving the C-O bond in alkyl ethers using dibromoboranes in the presence of a nickel catalyst and zinc reductant have been shown to simplify chemical syntheses and facilitate oxygen-to-nitrogen substitution or one-carbon homologation. Mechanistic studies have revealed a cleavage-then-rebound pathway via zinc/nickel tandem catalysis.