Croatica Chemica Acta, Vol. 99 No. 2, 2026.
Original scientific paper
https://doi.org/10.5562/cca4248
Exploiting the Reactivity of 2-Diazo-1,1,3,3,3-Pentafluoropropyl Phosphonate in [2,3]-Sigmatropic Rearrangement Reactions
Ita Hajdin
*
Romana Pajkert
Antonija Mravak
Jianlin Han
Gerd-Volker Röschenthaler
* Corresponding author.
Supplements: cca4248-supplement.pdf
Abstract
The Cu(II)-catalysed [2,3]-sigmatropic rearrangement of allyl and propargyl sulfides with the fluorinated diazo compound, 2-diazo-1,1,3,3,3-pentafluoropropyl phosphonate, has been investigated experimentally and computationally. The corresponding products 2 and 3a–d were obtained in yields of up to 79 %. Kinetic studies and DFT calculations indicate that Cu(I), generated in situ by reduction of Cu(II) with the diazo substrate, is the catalytically active species. The reaction proceeds via formation of a copper carbene and sulfonium ylide, which undergoes a facile [2,3]-sigmatropic rearrangement. These results expand the synthetic utility of fluorinated diazo compounds and provide mechanistic insight into the Doyle-Kirmse reaction under copper catalysis.
Keywords
diazo compound; [2,3]–sigmatropic rearrangement; DFT calculations; propargyl sulfide; allyl sulfide
Hrčak ID:
347315
URI
Publication date:
21.5.2026.
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