Radical Rearrangement Reaction of Propargyl Ethers to α,β-Unsaturated Aldehydes via Photoredox and Ni Catalysis

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 6, 2025

Aryl migration, especially 1,4-aryl is one of the most important reactions in radical rearrangement. Over past decades, migration by addition a to alkynes has become simple and efficient method difunctionalization alkynes. Radical-based aryl alkynoates been well-explored; however, propynyl ethers rarely studied. Herein, we first described propargyl ether valuable α,β-unsaturated aldehydes via photoredox Ni catalysis. This features redox-neutral conditions, readily available starting materials, broad substrate scope, good functional group compatibility, diverse transformations. Mechanistic studies suggest that this reaction proceeds through radical-involved pathway.

Language: Английский

Access to Spirocyclic Vinyl Sulfones via Radical Cyclization and Functional Group Migration

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Spirocyclic vinyl sulfones, which incorporate the three-dimensional structure inherent to spiro compounds and Michael acceptor reactivity associated with hold promise for novel biological activities. The lack of efficient synthetic methods, however, hinders their extensive investigations in drug discovery development. In this work, we describe a practical versatile approach synthesis multi-functionalized spirocyclic sulfones from easily available materials. reaction proceeds efficiently through cascade radical cyclization followed by (hetero)aryl migration. protocol features mild photocatalytic conditions provides access diverse range products, enabling construction complex scaffolds, including medium-sized ring-fused sulfones.

Language: Английский

The merger of electro-reduction and hydrogen bonding activation for a radical Smiles rearrangement

Chemical Science, Journal Year: 2024, Volume and Issue: 15(33), P. 13459 - 13465

Published: Jan. 1, 2024

An unprecedented radical smiles rearrangement of N -arylpropiolamides was realized by merging electro-reduction with hydrogen bonding activation. Enabled this dual activation strategy, the reduction potential shifted positively 218 mV.

Language: Английский