Affiliation:
1. Key Laboratory of Organofluorine Chemistry Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Lu Shanghai 200032 China
2. School of Chemistry and Material Sciences Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences 1 Sub-lane Xiangshan Hangzhou 310024 China
Abstract
AbstractThe 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(sp2)−F bond carbofunctionalization of refrigerant hydrofluoroolefins (HFOs) remains challenging. Here, we report a nickel‐catalyzed selective C(sp2)−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 Ni0(Ln) 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 PMe3, 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.
Funder
National Key Research and Development Program of China
National Natural Science Foundation of China
Subject
General Chemistry,Catalysis
Cited by
2 articles.
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