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The disposition of a polymeric prodrug of mitomycin C (MMC), mitomycin C-dextran conjugate (MMC-D), was studied in the single-pass perfused rat liver in order to clarify the effect of physico-chemical properties, such as molecular weight and electric charge, on the hepatic uptake of MMC-D. Six types of MMC-D were used: both cationic MMC-D (MMC-Dcat) and(More)
An asymmetric reductive aldol-type reaction of α,β-unsaturated esters with carbonyl compounds using Rh catalyst and Et2Zn was investigated. A chiral zinc complex from α,β-unsaturated ester was easily generated as the key intermediate from Et2Zn and Wilkinson's catalyst with diisopropyl L-(+)-tartrate to give a variety of enantioenriched β-hydroxy esters.(More)
Synthesis of alpha-CF(3) carbonyl compounds has been recognized to be difficult up to now because the polarization of CF(3)(delta-)-I(delta+) is opposite to that of CH(3)(delta+)-I(delta-), and this makes it difficult to introduce CF(3)(+) unit to enolates. We recently reported an effective alpha-trifluoromethylation of ketones by using Et(2)Zn with Rh(More)
An enantioselective Reformatsky reaction has been developed for the reaction of ethyl dibromofluoroacetate (1) with an imine. This method represents the first ligand-promoted imino-Reformatsky approach to use a halofluoroacetate. The use of an amino alcohol ligand allowed for the preparation of enantioenriched α-bromo-α-fluoro-β-lactams in good yields with(More)
A nickel-catalyzed Negishi coupling of bromodifluoroacetamides with arylzinc reagents has been developed. This reaction allows access to difluoromethylated aromatic compounds containing a variety of aryl groups and amide moieties. Furthermore, highly effective transformation of the functionalized difluoromethyl group (-CF2CONR(1)R(2)) was realized via(More)
Treatment of alpha,beta-unsaturated ketones with CF(3)I in the presence of Et(2)Zn and RhCl(PPh(3))(3) gave novel alpha-trifluoromethylation products in good yields. Hydrogen transfer from the ethyl group on the rhodium complex to the beta-position of the enone seems to play an important role in this reaction.
Oxidative Sonogashira cross-coupling reactions of (E)-trimethyl(3,3,3-trifluoroprop-1-enyl)silane with arylacetylene were achieved using silver fluoride and a palladium catalyst, to afford high yields of various 1,3-enynes with a CF3 group on the terminal sp(2) carbon. Silver fluoride promoted C-Si bond dissociation and oxidation of palladium, enabling(More)
A reaction between (E)-trimethyl(3,3,3-trifluoroprop-1-en-1-yl)silane (1) and arylaldehydes 2 was triggered by fluoride anions to afford aryl 3,3,3-trifluoropropyl ketones 3 in moderate to good yield. A mechanistic study of this reaction indicated that it occurred via an allyl alkoxide (4). A subsequent 1,3-proton shift of the benzylic proton of 4 forms 3.(More)
(E)-trimethyl-(3,3,3-trifluoroprop-1-enyl)silane (1) was synthesized as a reagent for use in Hiyama cross-coupling reactions for the production of β-trifluoromethylstyrene derivatives. Cross-coupling of 1 with electronically diverse aryl iodides was achieved by treatment with CsF in the presence of catalytic amounts of palladium to afford the desired(More)