Work

Iridium‐Catalyzed Enantioselective Intramolecular Hydroarylation of Allenes: Formal Synthesis of (+)‐Rhazinilam

Year: 2025

Type: article

Abstract: We report a versatile, highly enantioselective intramolecular hydroarylation of allenyl-tethered pyrroles and indoles. The reaction, promoted by an iridium(I)/bisphosphine chiral catalyst, provides a direct access heteropolycyclic systems bearing either tertiary or quaternary carbon stereocenters and a synthetically appealing alkenyl pendant. The method allows a highly efficient assembly of five-, six- and even seven-membered fused indole and pyrrole products, providing enantiomeric excesses of up to 99%. DFT computational studies align nicely with the experimental results and allow to rationalize the key factors that control both regio- and stereoselectivity of the process. Finally, the synthetic potential of the method was exemplified with a very short, highly enantioselective formal synthesis of (+)-Rhazinilam.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.202508252

Authors: Andrés Arribas, Alejandro Rey, Martín Calvelo, José L. Mascareñas, Fernando López

Institutions: Universidade de Santiago de Compostela, Centro Singular de Investigación en Química Biológica y Materiales Moleculares, Consejo Superior de Investigaciones Científicas, Misión Biológica de Galicia

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,510