Sulfonium-based precise alkyl transposition reactions.

Area of Science:

• Organic Chemistry
• Synthetic Chemistry
• Organosulfur Chemistry

Background:

• S-adenosyl-L-methionine (SAM) is a vital biological cofactor utilizing a sulfonium motif for methyl transfer.
• Nature's synthetic strategies involving sulfonium compounds inspire new chemical methodologies.

Purpose of the Study:

• To develop a novel aryne-activation strategy for alkyl group transposition.
• To design and synthesize robust sulfonium salts as electrophilic alkylation reagents.
• To demonstrate the synthetic utility in molecular editing and late-stage functionalization.

Main Methods:

• In situ generation of sulfonium intermediates from thioethers via aryne activation.
• Utilizing a TfO-incorporated [K(18-crown-6)] complex as a reaction promoter.
• Experimental and theoretical studies to elucidate reaction mechanisms.

Main Results:

• Demonstrated unique reactivity of sulfonium intermediates for alkyl group transposition.
• Developed a series of easily prepared sulfonium salts as effective electrophilic alkylation reagents.
• Achieved broad scope, excellent selectivity, and operational simplicity in the developed methods.

Conclusions:

• The presented aryne-activation strategy provides an efficient route for alkyl group transposition.
• The developed sulfonium salts are valuable reagents for complex molecule synthesis and modification.
• This approach holds significant potential for applications in medicinal chemistry and drug discovery.