Takamasa Fuchikami

A NOVEL AND CONVENIENT METHOD FOR TRIFLUOROMETHYLATION OF ORGANIC HALIDES USING CF3SIR'3/KF/CU(I) SYSTEM

Abstract Fluoride ion induced cross-coupling reaction of organic halides with trifluoromethyltrialkylsilanes takes place in the presence of Cu(I) salts under mild reaction conditions to give the corresponding trifluoromethylated products in high yields.

Transition-metal complex catalyzed polyfluoroalkylation. I. Facile addition of polyfluoroalkyl halides to carbon-carbon multiple bonds

Abstract Addition of polyfluoroalkyl halides to alkynes and alkenes bearing a variety of substituents is effected by the catalysis of iron, cobalt and ruthenium carbonyl complexes to give the corresponding adducts in good to excellent yields under mild conditions.

Transition-metal complex-catalyzed reduction of amides with hydrosilanes: a facile transformation of amides to amines

Abstract The reaction of amides with hydrosilanes is catalyzed by a variety of transition-metal complexes in the presence or absence of halides and amines as co-catalysts to afford the corresponding amines in good yields.

The reactions of hydrosilanes with trifluoropropene and pentafluorostyrene catalyzed by ruthenium, rhodium and palladium complexes

Abstract The reactions of hydrosilanes with trifluoropropene (TFP) and pentafluorostyrene (PFS) catalyzed by Ru3(CO)12 or RhCl(PPh3)3 give β-Rf-vinylsilane (1) and/or β-Rf-ethylsilane (2) (Rf = perfluorocarbon group). The 1/2 ratio is highly dependent on the nature of hydrosilane used. The ruthenium catalyst favors the formation of 1 compared with the rhodium catalyst. Neither α-Rf-vinylsilane nor α-Rf-ethyl-silane was formed at all. Possible mechanisms which can accommodate characteristic features of these reactions are discussed. The hydrosilylation of TFP with dichloro-methylsilane catalyzed by PdCl2(PhCN)2/2PPh3 gives the α-adduct (9a) exclusively, and this is transformed to the corresponding dialkoxysilanes, silane diol, oligosilane diols and cyclic oligosiloxanes.

Ruthenium complex catalyzed hydrosilylation of esters: a facile transformation of esters to alkyl silyl acetals and aldehydes

Abstract Hydrosilylation of esters takes place in the presence of ruthenium catalysts to afford the corresponding alkyl silyl acetals in moderate to good yields, which can be converted into aldehydes by hydrolysis.

Hydrogenation of amides by the use of bimetallic catalysts consisting of group 8 to 10, and group 6 or 7 metals

Abstract Hydrogenation of amides can be catalyzed by bimetallic systems. which consist of Group 8 to 10 late transition-metals and Group 6 or 7 early transition-metals. under the mild conditions to afford the corresponding amines selectively in good to excellent yields.

Facile syntheses of fluorine-containing α,β-unsaturated acids and esters from 2-trifluoromethylacrylic acid

Abstract Various types of fluorine-containing α,β-unsaturated acids and their esters were synthesized from 2-trilfuoromethylacrylic acid as a sole starting material.

Hydrogenation of carboxylic acids using bimetallic catalysts consisting of group 8 to 10, and group 6 or 7 metals

Abstract Hydrogenation of carboxylic acids to alcohols was effectively catalyzed by bimetallic systems consisting of Group 8 to 10 late transition-metals, and Group 6 or 7 early transition-metal carbonyls. These catalysts easily converted α,ω-dicarboxylic acid monoesters into ω-hydroxyalkanoic esters in good yields.

Photochemically generated silicon-carbon double-bonded intermidiates : II. Photolysis of aryldisilanes in the presence of dienes

Abstract Photolysis of eight aryldisilanes in the presence of 1,3-conjugated dienes (butadiene, isoprene and 2,3-dimethylbutadiene) has been studied. All of the aryldisilanes bearing a hydrogen on an ortho carbon atom in the aryl ring reacted upon UV irradiation with the conjugated dienes to give o -silyl-substituted (3-butenylsilyl)arene derivatives in high yields. The 13 C and 1 H NMR, and mass spectroscopic studies of the products are also described.

New synthetic route to N-acyl-α-amino acids via amidocarbonylation by means of homogeneous binary catalyst systems

Abstract New catalytic processes which lead to the formation of N -acyl-α-amino acids promoted by homogeneous binary systems are described: (a) the isomerization-amidocarbonylation of allyllic alcohols catalyzed by transition metal binary systems, e.g., Co-Rh, Co-Pd, Co-Fe, giving various aliphatic N -acyl-α-amino acids; (b) the isomerization-amidocarbonylation of oxiranes catalyzed by cobalt-Lewis acid systems giving N -acyl-α-amino acids: The process is extremely effective for the synthesis of N -acetylphenylalanine from styrene oxide and (c) the hydroformylation-amidocarbonylation of trifluoropropene catalyzed by cobalt-rhodium binary system giving N -acetyltrifluorovaline in excellent regioselectivity and yield. Possible mechanisms for these new processes are discussed.