Intermolecular Phosphite-Mediated Radical Desulfurative Alkene Alkylation Using Thiols.

Area of Science:

• Organic Chemistry
• Synthetic Methodology

Background:

• Thiols are versatile functional groups in organic synthesis.
• Generating carbon-centered radicals from thiols is synthetically valuable.
• Existing methods for thiol-based radical generation have limitations.

Purpose of the Study:

• To develop a new method for generating carbon-centered radicals from thiols.
• To establish a reductive coupling process utilizing these radicals.
• To explore the scope and limitations of the developed methodology.

Main Methods:

• A sulfur atom transfer process was developed using triethyl phosphite as the sulfur atom acceptor.
• Thiols were used as precursors for carbon-centered radicals.
• Reductive coupling reactions with various alkenes were performed.

Main Results:

• The developed process successfully generates carbon-centered radicals from thiols.
• A wide range of functionalized and electronically unbiased alkenes participate in the reductive coupling.
• The reaction proceeds via the exchange of weak S-H and C-S bonds for C-H, C-C, and S-P bonds.

Conclusions:

• A novel and efficient method for thiol-derived radical generation and subsequent reductive coupling has been established.
• This methodology offers a versatile approach for synthesizing complex molecules.
• The process is driven by favorable bond energy exchanges, highlighting its mechanistic basis.