Radical‐Mediated Hydroperfluoroalkylation of Unactivated Alkenes

Abstract

The direct hydroperfluoroalkylation of a wide range of unactivated alkenes has been achieved at room temperature with readily available iodoperfluoroalkanes using 4‐tert‐butylcatechol as a source of hydrogen atom and triethylborane. The hydrotrifluoromethylation could also be achieved under these conditions using gaseous trifluoromethyl iodide. An experimentally simple two‐step, one‐pot hydrotrifluoromethylation process using the easy‐to‐use trifluoromethanesulfonyl chloride as the source of trifluoromethyl radicals has also been developed. Using these two approaches, a broad range of substrates, including isoprenoid natural products, were efficiently derivatized.

Synthetic Utilization of 2H-Heptafluoropropane: Ionic 1,4-Addition to Electron-Deficient Carbon–Carbon Unsaturated Bonds

“…These methods use heptafluoro-2-iodopropane or hexafluoropropene as the reagent and introduce it into a carbon–carbon unsaturated bond (Scheme A). Heptafluoro-2-iodopropane can be added to unsaturated carbon–carbon bonds when exposed to light or one-electron reducing agents as part of a reaction. − Treatment of hexafluoropropene with metal fluorides followed by oxidation with one-electron oxidizing reagents produces a key intermediate for addition to unsaturated bonds . However, the conventional method faces the problem of homocoupling between radical species, where the heptafluoro-2-propyl group is introduced in the form of a radical species .…”