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

Area of Science:

• Synthetic Organic Chemistry
• Organoboron Chemistry

Background:

• Forming carbon-oxygen (C-O) and carbon-sulfur (C-S) bonds is crucial in synthetic organic chemistry.
• Existing methods often have limitations in scope or efficiency for creating diverse (thio)ethers and (thio)esters.

Purpose of the Study:

• To develop a versatile and modular approach for synthesizing structurally diverse (thio)ethers and (thio)esters.
• To expand the synthetic toolkit for accessing biologically relevant scaffolds.

Main Methods:

• Homologative coupling of α-halodiborylmethane with various oxygen- and sulfur-containing nucleophiles.
• Subsequent transformation of the diborylmethyl group via deborylative alkylation, Zweifel olefination, and boron-Wittig reactions.

Main Results:

• Demonstrated a broad substrate scope for the initial coupling reaction.
• Successfully diversified the diborylmethyl moiety to access various structural motifs.
• Efficiently generated diversely functionalized (thio)ethers and (thio)esters.

Conclusions:

• The developed protocol offers a versatile and modular strategy for synthesizing (thio)ethers and (thio)esters.
• This method expands the accessibility of biologically relevant scaffolds through efficient C-O and C-S bond formation.