Lewis Acid-Mediated Defluorination of Trifluoromethylarenes To Access Trivalent Phosphines
Abuduwaili Alimu1, Xiaoqiang Wu1, Siyu Song1
1Shanghai Key Laboratory of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, P. R. China.
Abstract:
Considering the strong inertness of the C-F bond, defluorinative functionalization of aromatic trifluoromethyl substrates has long been a formidable challenge, particularly with new functional groups introduced. Herein, we report a Lewis acid-mediated defluorinative transformation of aryl trifluoromethyl skeletons, enabling efficient access to trivalent phosphorus compounds. The reaction proceeds under simple conditions with high efficiency and broad substrate scope, and its demonstrated scalability further underscores its practical value. Moreover, aryl difluoro- and monofluoromethyl candidates can also undergo smooth conversion to the corresponding trivalent phosphines under these conditions, offering a novel protocol for the synthesis of phosphorus products.
Related Concept Videos
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction
Electrophilic Aromatic Substitution: Chlorination and Bromination of Benzene
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Carboxylic Acids to Acid Chlorides
Acid Halides to Carboxylic Acids: Hydrolysis
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic...


