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Updated: May 5, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Gold(I)-Catalyzed [2 + 2] and [3 + 2] Cycloadditions of 1,1-Difluoroallenes with Aldehydes: Switchable Syntheses of
Daisuke Miyazaki1, Konami Kudo1, Yusuke Fujiki1
1Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
Abstract:
1,1-Difluoroallenes underwent regioselective [2 + 2] and [3 + 2] cycloadditions with aldehydes using Au(I) catalysts. An AuCl catalyst enabled an α,β-selective [2 + 2] cycloaddition of 1,1-difluoroallenes, yielding (E)-3-alkylidene-2,2-difluorooxetanes. Conversely, an AuCl(IPr)-AgSbF6 catalyst facilitated an α,γ-selective [3 + 2] cycloaddition, followed by dehydrofluorination to produce aromatized 2-fluorofurans. DFT calculations (B3LYP level) suggested that the former reaction proceeded through Au(III)-containing metallacycles, while the latter involved cyclic Au(I) carbenoids.
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