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Updated: Oct 28, 2025

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Alkynyl triazenes enable divergent syntheses of 2-pyrones
Jin-Fay Tan1, Carl Thomas Bormann2, Kay Severin2
1Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305 CH-1015 Lausanne Switzerland nicolai.cramer@epfl.ch.
Abstract:
The 2-pyrone motif occurs frequently in bioactive natural products and is appreciated as synthetic intermediates. However, only few methods allow for diversifying functional group modifications on this relevant heterocycle. The distinct properties of 1-alkynyl triazenes promote a smooth addition of propiolic acids across the triple bond. Addition of catalytic amounts of silver salt induces cyclization to 2-pyrones. Depending on the reaction temperature, either 6-triazenyl or 5-triazenyl 2-pyrones are selectively formed. The triazenyl unit is subsequently replaced by a variety of valuable groups in a one-pot process yielding for instance 2-fluoro pyrones. The substitution occurs with an intriguing 1,5-carbonyl transposition. Moreover, the triazenyl group serves as traceless activating group for subsequent Diels-Alder cycloadditions and as a constituting unit for rare fused aminopyrazole pyrone heterocycles.
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