Ligand- and Temperature-Controlled Stereodivergent Nickel-Catalyzed Hydrophenoxylation of Ynamides
Abstract
The controlled synthesis of both E - and Z -stereoisomers remains a long-standing challenge in organic synthesis, yet it is important for accessing structurally and functionally diverse enamides. This study demonstrates the synthesis of E - and Z -hydrophenoxylated enamides using a nickel(II)-catalyst alongside phenols. The stereochemical outcome is controlled by the ligand environment and temperature. Ligands promote syn -addition via a keteniminium intermediate to afford the E -isomer, and elevated temperatures enable efficient E→Z isomerization to deliver the Z -isomer with excellent selectivity. This efficient and versatile strategy exhibits a broad substrate scope and functional group tolerance, including acids, bioactive estrone derivatives, sesamol, and related compounds.
Fields of Study & Subjects
Catalytic Alkyne Reactions
Catalytic C–H Functionalization Methods
Synthesis and Characterization of Pyrroles
Publication details
- Journal / source
- Organic Letters
- Publisher
- American Chemical Society (ACS)
- Volume
- 28
- Issue
- 7
- Pages
- 2494–2499
- Publication date
- 5 February 2026
- Language
- EN