Work

Merging Hydrogen‐Atom‐Transfer and the Truce‐Smiles Rearrangement for Synthesis of β‐Arylethylamines from Unactivated Allylsulfonamides

Year: 2025

Type: article

Abstract: Arylethylamines are crucial elements in pharmaceutical molecules, making methods for their synthesis highly significant. The Truce-Smiles rearrangement is a well-developed strategy to synthesize arylethylamine motifs via aryl migration. However, most examples require amide substrates to activate the alkene to attack by a radical precursor. This strategy both limits the product scope to amide-containing compounds as well as necessitating the incorporation of specific functional groups arising from the initial radical addition. In this work, we overcome these limitations, delivering a hydrogen-atom transfer from a cobalt catalyst to unactivated alkenes to yield β-arylethylamines with simple alkyl chains. DFT studies reveal that increasing the steric hindrance in at least one of the ortho positions on the migrating aromatic group promotes ipso over ortho addition, a selectivity that contrasts with previous methods.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.202418869

Authors: Hanqi Zhou, Danijela Lunic, Nil Sanosa, Diego Sampedro, Ignacio Funes‐Ardoiz, Christopher J. Teskey

Institutions: RWTH Aachen University, Technische Universität Braunschweig, Universidad de La Rioja

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,510