The development of effective strategies to forge C-O and C-S bonds in diverse chemical spaces is of considerable interest in synthetic organic chemistry. Herein we report a versatile approach for the modular synthesis of structurally diverse (thio)ethers and (thio)esters via homologative coupling of α-halodiborylmethane followed by transformation of the introduced diborylmethyl group. This method accommodates a wide array of oxygen- and sulfur-containing molecules, including biologically active compounds.
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