Synthesis of α-trifluoromethylstyrene derivatives via Ni-catalyzed cross-coupling of 2-bromo-3,3,3-trifluoropropene and aryl Grignard reagents

Chemoselective catalytic hydrodefluorination of trifluoromethylalkenes towards mono-/gem-di-fluoroalkenes under metal-free conditions

“…However, these reactions usually involve the preparation of complicated fluorinated precursors and are usually conducted under harsh conditions, e.g., in strongly basic solutions, thus leading to a quite limited substrate scope. One other good alternative could be defluorination of polyfluoroalkenes via transition-metal catalysis 40 – 45 , photocatalysis 46 – 49 , or the classical S N 2’ reactions 50 – 53 , delivering functionalized fluoroalkenes via alkenylation 54 , arylation 42 , borylation 55 , 56 , or hydrodefluorination (HDF) (Fig. 2b ) 45 .…”

Rapid access to diverse, trifluoromethyl-substituted alkenes using complementary strategies

“…5b – e Although several routes for preparing α-trifluoromethyl alkenes are reported, they are frequently lacking in functional group compatibility or ease of operation. Current approaches for the synthesis of this motif fall under three categories: (1) Wittig-type methylenation of trifluoromethyl ketones (TFMKs) under strongly basic conditions; 6 (2) Suzuki, Negishi, and Kumada cross-couplings that employ an arylboron species and highly volatile bromo-3,3,3-trifluoroprop-1-ene; 7 (3) Peterson-type olefination of TFMKs that utilizes a Grignard reaction in its synthetic sequence, thus limiting protic group tolerance. 8 …”

Recent advances in transition-metal catalyzed directed C–H functionalization with fluorinated building blocks

“…The trifluoromethylated building block, 2-bromo-3,3,3-trifluoropropene (BTP), is inexpensive, nonozone depleting [132][133][134][135] and one of the readily used building blocks for the introduction of an α-(trifluoromethyl)vinyl derivative into aromatic rings. [136][137][138][139][140] In this context, the directed C-H functionalization with BTP was realized by Bouillon and coworkers in 2016. 141 They developed a method to access α-(trifluoromethyl)styrene derivatives of anilides without prior prefunctionalization of the substrates through a Pd catalyzed C-H activation strategy.…”