O'Connor Thomas J, Toste F Dean
Department of Chemistry, University of California, Berkeley, California 04720, United States.
ACS Catal. 2018 Jul 6;8(7):5947-5951. doi: 10.1021/acscatal.8b01341. Epub 2018 Jun 4.
The gold(I)-catalyzed, stereoselective hydrofluorination of electron-deficient alkynes with triethylamine trihydrogen fluoride (EtN·3HF) is described. Fluorinated -unsaturated aldehydes, amides, esters, ketones, and nitriles were isolated in moderate to good yields as single diastereomers. In all but four cases, the ()-vinyl fluorides were initially formed in ≥97% diastereoselectivity. This work constitutes the first catalytic example of the diastereoselective preparation of a variety of -alkyl, -fluoro Michael acceptors from alkynes. Additionally, the described work expands access to -aryl, -fluoro Michael acceptors to the synthesis of -fluoro--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.
描述了金（I）催化的、用三乙胺三氟化氢（EtN·3HF）对缺电子炔烃进行立体选择性氢氟化反应。氟代α,β-不饱和醛、酰胺、酯、酮和腈以中等至良好的产率作为单一非对映异构体被分离出来。除了四个例子外，在所有情况下，（R）-乙烯基氟化物最初以≥97%的非对映选择性形成。这项工作构成了从炔烃非对映选择性制备各种α-烷基、β-氟代迈克尔受体的首个催化实例。此外，所描述的工作将α-芳基、β-氟代迈克尔受体的合成扩展到了α-氟代-α,β-不饱和酰胺和腈的合成。通过该策略形成的单氟烯烃很容易转化为其他含氟化合物，并且所开发的方法被应用于合成外用抗真菌药Exoderil的氟化类似物。
