Photoinduced Alkene Carbothiolation via Fe/Ni Dual Catalysis

Area of Science:

• Organic Chemistry
• Catalysis
• Sustainable Synthesis

Background:

• Alkene carbothiolation is valuable for C-C and C-S bond formation.
• Low-valent sulfur species often deactivate transition metal catalysts, hindering thioether synthesis.
• Direct C(sp3)-H activation of alkanes offers an atom-economical route to functionalized molecules.

Purpose of the Study:

• To develop a novel catalytic system for alkene carbothiolation using direct alkane C(sp3)-H activation.
• To overcome catalyst deactivation challenges associated with low-valent sulfur species.
• To provide a scalable and versatile method for synthesizing diverse thioethers.

Main Methods:

• Photoinduced Fe/Ni dual catalysis.
• Ligand-to-metal charge transfer (LMCT) for alkyl radical generation.
• Nickel-catalyzed cross-coupling and sulfide oxidation state modulation.
• Direct C(sp3)-H activation of simple alkanes.

Main Results:

• Successful alkene carbothiolation via direct C(sp3)-H alkane functionalization.
• Efficient formation of C-C and C-S bonds, yielding structurally diverse thioethers.
• Demonstrated broad functional group tolerance and good scalability of the method.
• Bypassed the need for prefunctionalized radical precursors and avoided catalyst deactivation.

Conclusions:

• The developed photoinduced Fe/Ni dual-catalytic system enables efficient alkene carbothiolation.
• This strategy provides a sustainable route to thioethers from abundant hydrocarbon feedstocks.
• The method offers a significant advancement in catalytic C-S bond formation and C-H functionalization.