Simple Synthesis of Fluorinated Ene-Ynes via In Situ Generation of Allenes

Fluorination of small molecules is a key route toward modulating reactivity and bioactivity. The 1,3 ene-yne functionality is an important synthon towards complex products, as well as a common functionality in biologically active molecules. Here, we present a new synthetic route towards fluorinated ene-ynes from simple starting materials. We employ gas chromatography-mass spectrometry analysis to probe the sequential eliminations necessary for this transformation and observe an allene intermediate. The ene-yne products are sufficiently fluorous to enable purification via fluorous extraction. This methodology will allow facile access to functional, fluorous ene-ynes.

Automated summary

Fluorination of small molecules is crucial for modulating reactivity and bioactivity. The 1,3 ene-yne functionality is important in synthesizing complex products and biologically active molecules. This study introduces a new synthetic route for fluorinated ene-ynes from simple starting materials, with gas chromatography-mass spectrometry analysis revealing the sequential eliminations necessary for this transformation.