Intercepting an avoided α-iminol rearrangement with a Petasis reaction for the synthesis of 2,3-diaryl substituted indoles
Abstract Rearrangement reactions are generally considered to be a rapid and synergistic intramolecular reconstructing process that is insensitive to intermolecular intruders. We report that α-iminol rearrangements could be strategically redirected by the interception of Petasis reactions, in the con...
Saved in:
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-05-01
|
| Series: | Communications Chemistry |
| Online Access: | https://doi.org/10.1038/s42004-025-01528-9 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | Abstract Rearrangement reactions are generally considered to be a rapid and synergistic intramolecular reconstructing process that is insensitive to intermolecular intruders. We report that α-iminol rearrangements could be strategically redirected by the interception of Petasis reactions, in the context of being avoided by strong electron-withdrawing groups on the migrative aryl units. 1,4-Aryl migration prevails over 1,2-aryl migration via forming a boron-ate complex. By leveraging this reactivity, we developed a regiospecific synthesis of unsymmetrically 2,3-diaryl substituted indoles from three readily available feedstocks: an amine, an arylglyoxal, and a boronic acid. While traditional Petasis reactions with similar three-component inputs are typically applied to build C(sp3)-C(sp2) and C(sp3)-C(sp3) bonds, the present transformation offers a special opportunity for constructing a C(sp2)-C(sp2) linkage. Highly substituted indole motifs with structural diversity in the C2 position are easily accessed by this three-component reaction. A mechanism containing a copper-cobalt collaborative promotion process was suggested. |
|---|---|
| ISSN: | 2399-3669 |