Diverse Synthesis of (Thio)ethers and (Thio)esters Using Halodiborylmethane as a Transformable C1 Building Block

Abstract

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. © 2024 American Chemical Society.