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Updated: Sep 8, 2025

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Alkylidene Carbene from Silyl Vinyl Iodide Provides Mechanistic Insights on Trimethylenemethane Diyl-Mediated Tandem
Dong Whan Jee1, Jinnie Myung2, R Daniel Little2
1Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Korea.
Abstract:
We describe a method to generate alkylidene carbenes via tetramethylammonium-fluoride-induced desilylation of silyl vinyl iodides. The reversible carbene generation from an iodovinyl anion enabled us to unearth mechanistic aspects of the trimethylenemethane (TMM) diyl cyclization reaction that could not be explored via previous methods. We observed that a slow diyl-diylophile cycloaddition can induce the reversible formation of an alkylidene carbene from the TMM diyl intermediate via a retro-cyclopropanation at ambient temperature.
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