Nickel‐Catalyzed Selective C(sp²)−F Bond Alkylation of Industrially Relevant Hydrofluoroolefin HFO‐1234yf

Abstract The selective transition‐metal catalyzed C−F bond functionalization of inexpensive industrial fluorochemicals represents one of the most attractive approaches to valuable fluorinated compounds. However, the selective C(sp 2 )−F bond carbofunctionalization of refrigerant hydrofluoroolefins (HFOs) remains challenging. Here, we report a nickel‐catalyzed selective C(sp 2 )−F bond alkylation of HFO‐1234yf with alkylzinc reagents. The resulting 2‐trifluoromethylalkenes can serve as a versatile synthon for diversified transformations, including the anti ‐Markovnikov type hydroalkylation and the synthesis of bioactive molecule analogues. Mechanistic studies reveal that lithium salt is essential to promote the oxidative addition of Ni 0 (L n ) to the C−F bond; the less electron‐rich N ‐based ligands, such as bipyridine and pyridine‐oxazoline, feature comparable or even higher oxidative addition rates than the electron‐rich phosphine ligands; the strong σ‐donating phosphine ligands, such as PMe 3 , are detrimental to transmetallation, but the less electron‐rich and bulky N ‐based ligands, such as pyridine‐oxazoline, facilitate transmetallation and reductive elimination to form the final product.