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Chromium(II)‐Catalyzed Stereoselective Cross‐Electrophile Coupling of Geminal Difluoroalkenes with Aliphatic Halides
Author(s) -
Hou Yunqian,
Zeng Xiaoming
Publication year - 2025
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202500129
Subject(s) - geminal , chemistry , stereoselectivity , electrophile , halide , catalysis , chromium , coupling (piping) , medicinal chemistry , organic chemistry , stereochemistry , mechanical engineering , engineering
Herein, an effective, mild, and practical approach to stereoselective cross‐electrophile coupling of difluoroalkenes with alkyl halides by cost‐effective chromium catalysis is reported. This reaction is promoted by inexpensive CrCl 2 combining with bipyridine ligand and manganese as the reductant, enabling the achievement of the reductive coupling of geminal difluoroalkenes with primary, secondary, and tertiary alkyl halides at ambient temperature. It provides a valuable and scalable approach to form tri‐substituted Z ‐fluoroalkylalkenes with good compatibility with a range of important functional groups. Preliminary mechanistic studies indicate that the coupling reaction is initiated by forming alkyl radical by addition to alkene and combining with Cr(II) or by coordination with Cr(II) and carbometallation of difluoroalkenes in giving (alkyl)Cr species, which converts to Z ‐alkylated fluoroalkene motifs in a stereoselective manner by elimination of β‐fluoride atoms.