Catalyst‐Free Preparation of Perfluoroalkyl‐Phosphoryl Substituted Furans from 1‐Perfluoroalkyl 1,3‐Diketones in Two Steps

Abstract

A two‐step catalyst‐free procedure for the construction of 3‐perfluoroalkyl‐2‐(phosphoryl)methyl furans from commercially available 1‐perfluoroalkyl 1,3‐diketones is reported. Propargylic alcohols, prepared by direct alkynylation of the diketones, react with PCl3 via [2,3]‐sigmatropic rearrangement – enolate cyclization sequence, leading to multifunctional furans. The reaction mechanism is supported by DFT study. In addition, the bioactivity modifying effect of phosphoryl group on 3‐perfluoroalkyl furans is depicted.magnified image

Towards tetrasubstituted furans through rearrangement and cyclodimerization of acetylenic ketones

“…The propargylic alcohols reacted with PCl 3 via a [2,3]-sigmatropic rearrangement and an enolate cyclization sequence, leading to multifunctional furans (Scheme 1a). 9 Later, Liang and co-workers described an iron( ii )-catalyzed cascade cycloisomerization reaction of readily accessible γ-hydroxyl ynones and diphenylphosphine oxides, resulting in bisphosphorylated dihydrofuran derivatives (Scheme 1b). 10 Very recently, our group disclosed an atom-economical approach to 2-phosphafurans by using simple 2-chloroethylphosphane and acetylenic ketones (Scheme 1c).…”