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. The initial coupling
exhibits a broad substrate scope, while subsequent diversification
of the diborylmethyl moiety enables access to various structural motifs
through deborylative alkylation, Zweifel olefination, and boron-Wittig
reaction. This protocol efficiently generates diversely functionalized
(thio)ethers and (thio)esters, expanding the toolkit for accessing
biologically relevant scaffolds.