- Merging Visible-Light Photocatalysis and Transition-Metal Catalysis in Three-Component Alkyl-Fluorination of Olefins with a Fluoride Ion
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The light-induced, Ru-catalyzed three-component alkyl-fluorination of olefins under mild reaction conditions is reported. This carbofluorination reaction features a wide substrate scope and good functional group tolerance. A key advantage of this photoredox reaction is the use of nucleophilic fluoride and generic alkyl groups. Late-stage functionalizations are achieved, and a copper-assisted oxidative quenching mechanism is proposed based on the mechanistic studies.
- Deng, Weili,Feng, Weiwei,Li, Yajun,Bao, Hongli
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- Combinatorial Nickel-Catalyzed Monofluoroalkylation of Aryl Boronic Acids with Unactivated Fluoroalkyl Iodides
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A combinatorial nickel-catalyzed cross-coupling between arylboronic acids and unactived 1-fluoro-1-iodoalkanes has been developed, which demonstrated high efficiency, mild conditions, and excellent functional-group compatibility. Readily available nitrogen and phosphine ligands were combined with a nitrogen source, which in situ generated a variety of easily tunable catalysts to promote the fluoroalkylation for broad scopes of both coupling partners. This new strategy on combinatorial catalysis offers new solutions for nickel-catalyzed cross-coupling reactions.
- Sheng, Jie,Ni, Hui-Qi,Liu, Ge,Li, Yan,Wang, Xi-Sheng
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- Nickel-Catalyzed Reductive Cross-Coupling of Aryl Halides with Monofluoroalkyl Halides for Late-Stage Monofluoroalkylation
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A combinatorial nickel-catalyzed monofluoroalkylation of aryl halides with unactivated fluoroalkyl halides by reductive cross-coupling has been developed. This method demonstrated high efficiency, mild conditions, and excellent functional-group tolerance, thus enabling the late-stage monofluoroalkylation of diverse drugs. The key to success was the combination of diverse readily available bidentate and monodentate pyridine-type nitrogen ligands with nickel, which in situ generated a variety of readily tunable catalysts to promote fluoroalkylation with broad scope with respect to both coupling partners. This combinatorial catalysis strategy offers a solution for nickel-catalyzed reductive cross-coupling reactions and provides an efficient way to synthesize fluoroalkylated druglike molecules for drug discovery.
- Sheng, Jie,Ni, Hui-Qi,Zhang, Hao-Ran,Zhang, Kai-Fan,Wang, Yi-Ning,Wang, Xi-Sheng
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supporting information
p. 7634 - 7639
(2018/06/26)
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- Behaviors of α-Fluorocarbenoids Derived from the Nucleophilic Desulfinylation of α-Chloro-α-fluoroalkyl Sulfoxides
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2-Aryl-1-chloro-1-fluoroethyl sulfoxides underwent nucleophilic desulfinylation with PhMgBr to give (Z)-fluorostyrene derivatives in a very stereoselective manner (>33:1) via an α-fluorocarbene species.When treated with 3 equiv of PhLi in the presence of N,N,N',N'-tetramethylethylenediamine, they similarly formed fluorostyrenes as a stereoisomeric mixture (E:Z = 2:1), but with 1 equiv of PhLi 1-aryl-1-chloro-1-fluoroethanes were the major product.On the other hand, no formation of a fluoroalkene was observed in the desulfinylation of 1-chloro-1-fluoro-4-phenylbutyl sul foxide with the nucleophiles.In the latter reaction, oxidation and/or phenylation of the intermediate carbene were the main pathways.
- Uno, Hidemitsu,Sakamoto, Katsuji,Semba, Fumihiko,Suzuki, Hitomi
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p. 210 - 217
(2007/10/02)
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