1,2-Bis(arylthio)arene synthesis via aryne intermediates

Area of Science:

• Organic Chemistry
• Synthetic Methodology
• Organosulfur Chemistry

Background:

• Arynes are highly reactive intermediates crucial in organic synthesis.
• Disulfide bonds are versatile functional groups with diverse applications.
• Developing efficient methods for aryne insertion into S-S bonds remains a synthetic challenge.

Purpose of the Study:

• To develop a novel method for the direct insertion of arynes into disulfide S-S bonds.
• To explore the utility of Lithium 1,1-diadamantylamide (LDAM) as a base for promoting this transformation.
• To investigate the scope and limitations of the developed reaction with various disulfides and aryne precursors.

Main Methods:

• Generation of arynes from readily available aryl halides and triflates.
• Utilizing Lithium 1,1-diadamantylamide (LDAM) as the base catalyst.
• Reaction of in situ generated arynes with diaryl and diisopropyl disulfides.
• Characterization of the resulting insertion products using standard spectroscopic techniques.

Main Results:

• Successful insertion of arynes into disulfide S-S bonds was achieved.
• Reactions afforded the desired insertion products in moderate to excellent yields.
• The use of 1-cyclohexenyl triflate resulted in an excellent yield of 1,2-bis(phenylthio)cyclohexene.
• The LDAM base effectively promoted the aryne insertion reaction.

Conclusions:

• Lithium 1,1-diadamantylamide (LDAM) is an effective base for promoting aryne insertion into disulfide S-S bonds.
• The developed method offers a new and efficient pathway for synthesizing organosulfur compounds.
• This methodology provides a valuable tool for synthetic chemists exploring novel bond formations.