Diverse Synthesis\nof (Thio)ethers and (Thio)esters\nUsing Halodiborylmethane as a Transformable C<sub>1</sub> Building\nBlock

The development of effective strategies to forge C–O\nand\nC–S bonds in diverse chemical spaces is of considerable interest\nin synthetic organic chemistry. Herein we report a versatile approach\nfor the modular synthesis of structurally diverse (thio)ethers and\n(thio)esters via homologative coupling of α-halodiborylmethane\nfollowed by transformation of the introduced diborylmethyl group.\nThis method accommodates a wide array of oxygen- and sulfur-containing\nmolecules, including biologically active compounds. The initial coupling\nexhibits a broad substrate scope, while subsequent diversification\nof the diborylmethyl moiety enables access to various structural motifs\nthrough deborylative alkylation, Zweifel olefination, and boron-Wittig\nreaction. This protocol efficiently generates diversely functionalized\n(thio)ethers and (thio)esters, expanding the toolkit for accessing\nbiologically relevant scaffolds.