Manabu Kuroboshi

Zinc-copper(I) chloride or -silver(I) acetate promoted aldol reaction of chlorodifluoromethyl ketones with carbonyl compounds. A general and effective route to α,α-difuluoro-β-hydroxy ketones

Abstract Chlorodifluoromethyl ketones efficiently underwent the aldol reaction with a variety of aldehydes or ketones in the presence of zinc, a catalytic amount of copper(I) chloride or silver(I) acetate and molecular sieves to give the corresponding α,α-difluoro-β-hydroxy ketones in good to excellent yields.

Stereoselective synthesis of (E)-ArCFCFR and (E)-ArCHCFR from ArCH(OH)CFBr2

Abstract ( E )- vic -Difluoro olefin, RCFCFBr, was synthesized by dehydrobromination of RCFHCFBr 2 using lithium 2,2,6,6-tetramethylpiperidide. ( E )-Fluoro olefin, RCHCFBr, was obtained by treatment of RCH(OAc)CFBr 2 with EtMgBr and HN( i -Pr) 2 .

Palladium catalyzed cross-coupling reaction of functionalized alkyltrifluorosilanes with aryl halides

Abstract A variety of alkyltrifluorosilanes were found to couple with aryl halides in the presence of Pd(PPh3)4 catalyst and tetrabutylammonium fluoride (TBAF) to give the corresponding cross-coupled products in moderate to good yields.

A convenient synthesis of perfluoroalkylated amines by oxidative desulfurization-fluorination

Abstract N -Perfluoroalkylamines were synthesized from perfluoroalkanethioamides, which were easily accessible from perfluoroalkanamides, by the action of N -halo imide and n Bu 4 NH 2 F 3 .

Addition reactions of F-alkyl iodides to carbon-carbon double bonds promoted by metallic tin(0)-metal salt systems

Abstract F -alkyl iodides readily reacted with a variety of alkenes in methanol at room temperature under the influence of metallic tin(0)-silver(I) acetate of metallic tin(0)-copper(I) chloride to afford the corresponding addition products, F - alkylated iodides, in good to excellent yields. This addition reaction was also promoted by the use of a metallic tin(0)- aluminium(0) reagent, though gentle heating was necessary for allowing the reaction to proceed.

Synthesis of trifluoromethylamino-substituted pyridines and pyrimidines by oxidative desulfurization-fluorination

Abstract Oxidative desulfurization-fluorination of methyl N -pyridyl(or N -pyrimidyl)- N -alkyldithiocarbamates gave the corresponding trifluoromethylamino-substituted pyridines (or pyrimidines), which underwent cross-coupling reaction to give a new type of liquid crystalline compounds having trifluoromethylamino group.

Catalytic asymmetric hydrosilylation of 1,3-dienes with difluoro(phenyl) silane

Abstract A palladium complex with an optically active ligand catalyzes asymmetric hydrosilylation of 1,3-dienes using difluoro(phenyl)silane to give optically active allyl difluoro(phenyl)silanes in good enantiomeric excess.

Synthesis of perfluoroalkyl-substituted arenes by oxidative desulfurization-fluorination

Abstract Perfluoroalkyl-substituted arenes have been readily synthesized from 2-aryl-2-perfluoroalkyl-1,3-dithiolanes by the action of an N -halo imide and HF/pyridine (or HF/melamine).

Zinc-copper(I) chloride or -silver acetate promoted coupling reaction of 2-[(Trimethylsilyl)methyl]-3-chloro-3,3-difluoropropene with carbonyl compounds. Highly efficient access to 2,2-difluoro homoallyl alcohols

Abstract 2-[(Trimethylsilyl)methyl]-3-chloro-3,3-difluoropropene, readily prepared in two steps from methyl chlorodifluoroacetate and (trimethylsilyl)methylmagnesium chloride, is reduced to couple regioselectivity with a variety of carbonyl compounds in the presence of zinc-copper(I) chloride or -silver acetate to give 2,2-difluoro-3-[(trimethylsilyl)methyl]-3-buten-1-ol derivatives in good to excellent yields.

A new efficient method for the generation of F-alkyl ketone metal enolates by using copper(II) bromide-lithium aluminium hydride reagent and their aldol reaction with carbonyl compounds

Abstract 1-Substituted F -1-alkenyl phosphates, readily prepared from F -alkyl ketones and sodium diethyl phosphite, were treated with copper(II) bromide-lithium aluminium hydride reagent at −30 °C to generate in situ F -alkyl ketone aluminium enolates, which underwent the aldol reaction with various aldehydes to give the corresponding α-fluoro-α- F -alkyl β-hydroxy ketones in fairly good to excellent yields.