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Updated: Oct 26, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers
Conor E Brigham1, Christian A Malapit1, Naish Lalloo1
1Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
Abstract:
This report describes the development of a nickel-catalyzed decarbonylative reaction for the synthesis of fluoroalkyl thioethers (RFSR) from the corresponding thioesters. Readily available, inexpensive, and stable fluoroalkyl carboxylic acids (RFCO2H) serve as the fluoroalkyl (RF) source in this transformation. Stoichiometric organometallic studies reveal that RF-S bond-forming reductive elimination is a challenging step in the catalytic cycle. This led to the identification of diphenylphosphinoferrocene as the optimal ligand for this transformation. Ultimately, this method was applied to the construction of diverse fluoroalkyl thioethers (RFSR), with R = both aryl and alkyl.
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