| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1313734 | Journal of Fluorine Chemistry | 2015 | 8 Pages |
•Structure–reactivity-relationship study of this reaction was investigated.•Chelation of alkoxide and fluorine to the lithium ion plays a crucial role.•Theoretical investigation was examined for supporting the proposed mechanism.
We previously found that treatment of (Z)-trifluoromethylated-2-aryl allylic alcohols with organolithium provided the SN2′-type product through CO bond cleavage. Interestingly, no additive was required to enhance the nucleophilicity of the organolithium, and the free hydroxyl group served as a leaving group. The mechanistic studies of the unique transformation indicated that chelation of alkoxide and fluorine of the trifluoromethyl group to the lithium ion play a crucial role in controlling the reactivity and selectivity. Furthermore, theoretical investigation supported this interpretation.
Graphical abstractMechanistic study on SN2′-type reaction of (Z)-trifluoromethylated allylic alcohol with organolithium reagent was examined.Figure optionsDownload full-size imageDownload as PowerPoint slide
