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

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Science  09 Apr 2021:
Vol. 372, Issue 6538, pp. 175-182
DOI: 10.1126/science.abg5526

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Slipping boron into alkyl ethers

The carbon–oxygen bonds that hold alkyl ethers together are relatively inert. Lyu et al. report that zinc and nickel can team up to insert boron between the carbon and oxygen using an unusual mechanism. First, a dibromoborane pries open the bond with help from a zinc ion. Next, the nickel stitches together the carbon and boron, and the oxidation of metallic zinc starts the cycle over again. Versatile reactivity at the inserted boron center can then add carbons to the original ether or swap out oxygen for nitrogen.

Science, this issue p. 175

Abstract

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.

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