Trifluoromethylation of aliphatic halides with trifluoromethyl copper

A solution of trifluoromethyl copper complex in hexamethylphosphoric triamide was found to be useful for trifluoromethylation of aliphatic halides.     

The synthesis of new valence-bond isomers of pentakis(trifluoromethyl)-1,3-diazepine

A new valence-bond isomer of pentakis(trifluoromethyl)-1,3-diazepine was synthesized from tris(trifluoromethyl)cyclopropenyl trifluoromethyl ketone, and reacted with diazomethane to give an N-methylated product.     

Direct synthesis of 1,3-diketones by Rh-catalyzed reductive alpha-acylation of enones

1,3-Diketones were synthesized from alpha,beta-unsaturated ketones by treatment with acid chlorides and Et(2)Zn in the presence of RhCl(PPh(3))3. This is a very simple and extremely chemoselective reaction to give the adduct at the alpha-position of alpha,beta-unsaturated ketones.     

Asymmetric reduction of perfluoroalkyl ketones with chiral lithium alkoxides

Reduction of perfluoroalkyl ketones with chiral lithium alkoxides gave chiral α-perfluoroalkyl alcohols in high enantiomeric excesses. Interestingly, reaction of 2,2,2-trifluoroacetophenone (1) with lithium (S)-1-phenylethoxide (2) gave (S)-2,2,2-trifluoro-1-phenylethanol (3), while the same reaction of perfluorooctan-1-one (7) with 2 gave (R)-1H-1-phenylperfluorooctanol (8). Based on the speculation of mechanism, the order of steric effects on this reaction is estimated as C₇F₁₅ > substituted phenyl > CF₃.     

Novel reduction of perfluoroalkyl ketones with lithium alkoxides

The reaction of tert-butyl N-(2-bromophenyl)carbamate (1) with ethyl perfluorooctanoate in the presence of tert-butyllithium did not give the desired N-(2-perfluorooctanoylphenyl)carbamate (3) but gave 1-hydroxy-1H-perfluorooctyl compound (4), which was supposed to be formed by the reduction of 3. A similar reaction of 2,2,2-trifluoroacetophenone with tert-butyllithium did not gave any reduction product. Detailed investigation showed that lithium ethoxide worked as the reducing agent of this abnormal reduction. By the reaction of lithium isopropoxide, an aldol product from 2,2,2-trifluoroacetophenone with acetone was isolated, while perfluoroheptyl or perfluoropropyl phenyl ketones were reduced by this alkoxide in a high yield without formation of the aldol adduct.     

One-pont synthesis of 5-fluoro-6-alkoxy-5,6-dihydrouracils

Fluorine diluted with argon was bubbled into a suspension of uracil in acetic acid at room temperature. Treatment of the reaction mixtur with alcohols gave 5-fluoro-6-alkoxy-5,6-dihydrouracils, which lost alcohols on sublimation under vacuum to give 5-fluorouracil quantitatively.     

Reaction of trist(trifluoromethyl)cyclopropenyl trifluoromethyl ketone with azo compounds in the presence of triphenylphosphine,and synthesis of tetrakis(trifluoromethyl)pyridazine.

The title cyclopropenylketone reacts with azo compounds and tri-phenylphosphine to give unique heterocycles; tricyclourazoles and a diazaoxacyclooctatriene. The formers were converted into a pyridazine.