95392-04-4Relevant academic research and scientific papers
Organo-catalyzed Michael addition of 2-fluoro-2-arylacetonitriles
Chen, De-Yin,Song, Shuai,Chen, Ling-Yan,Ren, Xinfeng,Li, Ya
supporting information, (2021/03/01)
An efficient synthesis of a variety of 2-arylacetonitriles containing a fluorinated stereogenic center through organo-catalyzed Michael addition reaction of 2-fluoro-2-arylacetonitriles has been developed. This protocol uses a cheap organocatalyst (DBU) and has a broad substrate scope: α, β-unsaturated ketones, esters, nitriles and sulfones were all successfully reacted. Importantly, water proved to be a good solvent for this reaction.
Enantioselective hydrolysis of (RS)-2-fluoroarylacetonitriles using nitrilase from Arabidopsis thaliana
Effenberger, Franz,Osswald, Steffen
, p. 279 - 285 (2007/10/03)
The enzymatic resolution of 2-fluoroarylacetonitriles (RS)-3 using nitrilase from the plant Arabidopsis thaliana is described. Racemic 2-fluoronitriles 3 are easily accessible from O-silylated aromatic cyanohydrins 2 by reaction with DAST. The nitriles (RS)-3 were hydrolysed with the nitrilase as a catalyst, not to the expected 2-fluoroarylacetic acids but to the corresponding (R)-2-fluoroarylacetamides (R)-5 as the main products. After optimization of reaction conditions (pH 9, 7°C), the enantiomeric excesses of (R)-5a,c and f (R=H, 3-Me, 3-OMe) could be improved to >99% by one recrystallization. The acid catalysed hydrolysis of (R)-5a,5c and 5f afforded the corresponding (R)-2-fluoroarylacetic acids (R)-4a,4c and 4f without racemization.
Selective, Electrophilic Fluorinations Using N-Fluoro-o-benzenedisulfonimide
Davis, Franklin A.,Han, Wei,Murphy, Christopher K.
, p. 4730 - 4737 (2007/10/02)
The synthesis of N-fluoro-o-benzenedisulfonimide (NFOBS, 2) and its use as an "electrophilic" fluorinating reagent with nucleophilic substrates is described and compared with that of N-fluorobenzenesulfonimide (NFSi, 3).NFOBS (2) is prepared in three steps in 81percent overall yield from commercially available o-benzenedisulfonic acid (4) and involves treatment of o-benzenedisulfonimide (6) with dilute fluorine (10percent F2/N2).Reaction of 2 with metal enolates, silyl enol ethers, and 1,3-dicarbonyl compounds affords the corresponding α-fluoro compounds in yields up to 95percent, with good control of mono- and difluorination.Fluorination of ortho-metalated aromatic compounds was achieved in modest to good yields (10-80percent).While the reactivities of 2 and 3 are similar, better yields were observed with the former reagent in the fluorination of metal enolates, Grignard and lithium reagents, while 3 gave better results with the ortho-lithiated aromatic substrates.The available evidence suggests an SN2-type mechanism for the fluorination of nucleophilic substrates by these reagents.
A NOVEL SYNTHESIS OF α-FLUOROOACETONITRILES. APPLICATION TO A CONVENIENT PREPARATION OF 2-FLUORO-2-PHENETYLAMINES
LeTourneau, Michael E.,McCarthy, James R.
, p. 5227 - 5230 (2007/10/02)
α-Fluorophenylacetonitriles (3) are readily prepared by the treatment of the corresponding benzaldehyde cyanohydrin trimethylsilylethers (2) with diethylaminosulfur trifluoride (DAST).This method for the introduction of fluorine alpha to the cyano group is also applicable to the cyanohydrin trimethylsilylethers of aromatic ketones.Diborane reduction of the α-fluorophenylacetonitriles (3) yields 2-fluoro-2-phenethylamines (4).
