Fluoroalkylation of Allylic Alcohols with Concomitant (Hetero)aryl Migration: Access to Fluoroalkylated Ketones and Evaluation of Antifungal Action against Magnaporthe grisea

• Published in: European journal of organic chemistry Vol. 2020; no. 32; pp. 5192 - 5200
• Main Authors: Zhang, Yanhu, Ren, Ziyang, Liu, Yun‐Lin, Wang, Zhentao, Li, Zhaodong
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 31.08.2020
• Subjects: Alcohols; Alkenes; Allylic alcohols; Aromatic compounds; Aryl migration; Copper; Fluorine; Fungicides; Ketones; Perfluoroalkyl & polyfluoroalkyl substances; Radicals
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202000782

Fluoroalkyl(hetero)arylation of allylic alcohols with perfluoroalkyl iodide or difluoroacetic acid as fluoroalkyl source was developed herein, delivering functionalized ketones containing an α‐quaternary center. Formation of the fluoroalkyl radical was followed by its intermolecular addition to alkenes and the migration of a (hetero)aryl group with the concomitant generation of a ketone group to finish the domino sequence. Mechanistic studies indicated that the aryl migration proceeded through neophyl rearrangement in a radical pathway. Moreover, preliminary antifungal evaluation against Magnaporthe grisea is also described for the first time. Fluoroalkyl(hetero)arylation of allylic alcohols with perfluoroalkyl iodide and difluoroacetic acid as coupling partners is reported herein. Mechanistic studies disclosed that the aryl migration proceeded through neophyl rearrangement in a radical pathway controlled by radical polarity. Moreover, promising antifungal activity against Magnaporthe grisea is also described for the first time.