Pinacol coupling reaction of beta-halo-alpha,beta-unsaturated aldehydes promoted by TiI4

The pinacol reaction of beta-halogenated alpha,beta-unsaturated aldehydes was promoted by titanium tetraiodide to give coupling products in good yields with high dl-selectivity. Subsequent reduction with H(2)/Pd-C gave saturated vic-diols in good yields. Heck coupling reaction enabled the displacement of halogens with vinyl groups without the loss of stereochemical integrities. [reaction: see text]     

Chiral β-dimethylaminoalkylphosphines. Highly efficient ligands for a nickel complex catalyzed asymmetric grignard cross-coupling reaction

Chiral β-dimethylaminoalkylphosphines were prepared starting with amino acids, (S)-alanine, (S)-phenylalanine, (R)-phenylglycine, (S)-valine, and (R)-tert-leucine. The chiral phosphines were found to be highly efficient ligands for a nickel catalyzed asymmetric Grignard cross-coupling reaction (38～94% optical yield).     

Progress toward the total synthesis of ciguatoxins: a convergent synthesis of the FGHIJKLM ring fragment

[structure: see text] A highly convergent synthetic route to the FGHIJKLM ring fragment of ciguatoxins has been developed, which relied on extensive use of the B-alkyl Suzuki-Miyaura coupling reaction.     

A new method for the evaluation of the relative stability of organosulfur radicals by competitive elimination technique

The relative stability of various organosulfur radicals is estimated by competitive elimination technique using tributyltin radical and acetophenone derivatives having two different sulfur substituents at α and α positions.     

Photochemically generated silicon-carbon double-bonded intermediates VIII. Photolysis of phenyldisilane derivatives in the presence of olefins

Photolysis of phenylpentamethyldisilane, 1,1-diphenyltetramethyldisilane and 1-isopropyl-1-phenyltetramethyldisilane in the presence of a wide variety of olefins has been studied. All reactions investigated, with the exception of those with 1-methylcyclohexene and tetramethylethylene, afforded the corresponding 1/1 addition products. Yields of the adducts depended highly on the structure of the olefins used. In the photolysis of phenylpentamethyldisilane in the presence of an equimolar mixture of 1,1- and 1,2-bis(trimethylsilyl)ethene under competitive reaction conditions, the main product was the one arising from the 1,1-isomer. A possible mechanism for the process of addition of olefin to the photochemically generated silicon-carbon double-bonded intermediate (A) is discussed.     

Phase Relations in the Ni–Mn–Ga Ternary System and Aging Effect on Shape Memory Properties of Ferromagnetic Ni<Subscript>2</Subscript>MnGa Sputtered Films

Summary. Isothermal sections of the Ni–Mn–Ga ternary phase diagram at 1073 and 1273 K were investigated over a wide range of alloy compositions. The range of the β-Ni₂MnGa phase, its equilibria with the γ-(Mn, Ni), α′-Ni₃Ga, and γ-Ni₃Ga₂ phases, and the liquidus and solidus lines were determined experimentally. The aging effect on the shape memory effect (SME) of Ni₂MnGa sputtered films was also investigated. The two-way SME of the constraint-aged films was confirmed by the temperature change.     

Total synthesis of gambierol

[structure: see text] The first total synthesis of gambierol, a marine polycyclic ether toxin, has been achieved. The synthesis features the Pd(PPh3)4/CuCl/LiCl-promoted Stille coupling for the stereoselective construction of the sensitive triene side chain that includes a conjugated (Z,Z)-diene moiety.     

Silicon hydrides and nickel complexes : III. Hydrosilylation of olefins with dichloro[1,2-bis-(dimethylphosphino)-1,2-dicarba-closo-dodecaborane]-nickel(II) as catalyst

The hydrosilylation of olefins catalyzed by nickel(II) chloride complexed with 1,2-bis(dimethylphosphino)-1,2-dicarba-closo-dodecaborane produces terminal and internal adducts in comparable amounts. This unusual feature of the reaction is explained in terms of the electron-accepting nature of the carboranyl group.     

Energy funneling of IR photons captured by dendritic antennae and acceptor mode specificity: anti-stokes resonance raman studies on iron(III) porphyrin complexes with a poly(aryl ether) dendrimer framework

A series of poly(aryl ether) dendrimer chloroiron(III) porphyrin complexes (LnTPP)Fe(III)Cl (number of aryl layers [n]=3 to 5) were synthesized, and their Boltzmann temperatures under IR irradiation were evaluated from ratios of Stokes to anti-Stokes intensities of resonance Raman bands. While the Boltzmann temperature of neat solvent was unaltered by IR irradiation (LnTPP)Fe(III)Cl (n=3 to 5), all showed a temperature rise that was larger than that of the solvent and greater as the dendrimer framework was larger. Among vibrational modes of the metalloporphyrin core, the temperature rise of an axial Fe-Cl stretching mode at 355 cm-1 was larger than that for a porphyrin in-plane mode at 390 cm-1. Although most of the IR energy is captured by the phenyl nu8 mode at 1597 cm-1 of the dendrimer framework, an anti-Stokes Raman band of the phenyl nu8 mode was not detected, suggesting the extremely fast vibrational relaxation of the phenyl mode. From these observations, it is proposed that the energy of IR photons captured by the aryl dendrimer framework is transferred to the axial Fe-Cl bond of the iron porphyrin core and then relaxed to the porphyrin macrocycle.     

Homogeneous palladium catalyst suppressing Pd black formation in air oxidation of alcohols

In homogeneous catalyst systems, there is the persistent problem that metal aggregation and precipitation cause catalyst decomposition and considerable loss of catalytic activity. Pd black formation is a typical example. Pd catalysts are known to easily aggregate and form Pd black, although they realize a wide variety of useful reactions in organic synthesis. In order to overcome this intrinsic problem of homogeneous Pd catalysis, we explored a new class of Pd catalyst by adopting aerobic oxidation of alcohols as a probe reaction. Herein we report a new catalyst system that suppresses the Pd black formation even under air and with a high substrate to catalyst molar ratio (S/C: more than 1000) in oxidation of alcohols. The novel pyridine derivatives having a 2,3,4,5-tetraphenylphenyl substituent and its higher dendritic unit at the 3-position of the pyridine ring were found to be excellent ligands with Pd(OAc)2 in the palladium-catalyzed air (balloon) oxidation of alcohols in toluene at 80 degrees C. Comparison with structurally related pyridine ligands revealed that introduction of the 2,3,4,5-tetraphenylphenyl substituent at the 3-position of pyridine ring effectively suppresses the Pd black formation, maintaining the catalytic activity for a long time to give aldehydes or ketones as products in high yields.