Gold-Catalyzed Hydrofluorination of Electron-Deficient Alkynes: Stereoselective Synthesis of β‑Fluoro Michael Acceptors Thomas J. O’Connor F. Dean Toste 10.1021/acscatal.8b01341.s001 https://acs.figshare.com/articles/journal_contribution/Gold-Catalyzed_Hydrofluorination_of_Electron-Deficient_Alkynes_Stereoselective_Synthesis_of_Fluoro_Michael_Acceptors/6432176 The gold­(I)-catalyzed, stereoselective hydrofluorination of electron-deficient alkynes with triethylamine trihydrogen fluoride (Et<sub>3</sub>N·3HF) is described. Fluorinated α,β-unsaturated aldehydes, amides, esters, ketones, and nitriles were isolated in moderate to good yields as single diastereomers. In all but four cases, the (<i>Z</i>)-vinyl fluorides were initially formed in ≥97% diastereoselectivity. This work constitutes the first catalytic example of the diastereoselective preparation of a variety of β-alkyl, β-fluoro Michael acceptors from alkynes. Additionally, the described work expands access to β-aryl, β-fluoro Michael acceptors to the synthesis of β-fluoro-α,β-unsaturated amides and nitriles. The monofluoroalkenes formed through this strategy were readily transformed into other fluorine-containing compounds, and the developed method was applied to the synthesis of a fluorinated analogue of Exoderil, a topical antimycotic. 2018-06-04 20:13:39 β- aryl Stereoselective Synthesis synthesis triethylamine trihydrogen fluoride Gold-Catalyzed Hydrofluorination fluorine-containing compounds β- fluoro Michael acceptors electron-deficient alkynes nitrile β- alkyl amide Electron-Deficient Alkynes diastereoselective preparation