The synthesis and characterization of titanium complexes of the aryloxido-functionalized N-heterocyclic carbene ligand (L) is reported, in which the tridentate L ligand meridionally coordinates to the metal center.
Butylation problems ironed out: 3‐Pentynyl ethers react with butyllithium at −20°C in toluene, upon addition of a catalytic amount of a cheap iron(III) salt, to afford (E)‐4‐methyl‐3‐octenyl ethers in high yields. Stereochemically defined tetrasubstituted alkenes were also obtained by the subsequent addition of electrophiles (E+, see scheme; acac = acetylacetonate, Bn=benzyl).
In the cardiomyopathic hamsters with CHF, the production of ET-1 in the heart was markedly increased, and chronic ETA receptor blockade greatly ameliorated survival and cardiac dysfunction. These results suggest that ET-1 plays an important role in the deterioration of CHF caused by cardiomyopathy, and ETA antagonists may exert therapeutic effects in CHF due to cardiomyopathy.
Difluorinated polycyclic aromatic hydrocarbons (PAHs) containing three to five benzene rings were systematically synthesized by the Pd(II)-catalyzed Friedel-Crafts-type cyclization of 1,1,2trifluoro-and 1,1-difluoro-1-alkenes and the In(III)-catalyzed tandem cyclization of bis(1,1difluoroallene)s. Using an array of the difluorinated PAHs that were obtained and previously reported monofluorinated PAHs, the physical properties of the pinpoint-fluorinated PAHs were investigated. (i) The 19 F NMR signals of the bay-region fluorine atoms were shifted downfield by ca. 8-14 ppm for vicdifluorinated PAHs and ca. 11-19 ppm for non-vic-difluorinated and monofluorinated PAHs. (ii) The introduction of fluorine into PAH molecules increased their solubilities in organic solvents, which was best exemplified by the high solubilities of 6,7-difluoropicene (5.4 wt%) and 6-fluoropicene (5.3 wt%) in THF. (iii) The HOMO-LUMO energy gaps of the pinpoint-fluorinated PAHs were smaller than that
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