Synthesis and structure of 16 pi octaalkyltetraphenylporphyrins

The oxidized octaethyltetraphenylporphyrin (1, OETPP) and the corresponding newly prepared octaisobutyltetraphenylporphyrin (3, OisoBuTPP) could be isolated from the reaction of OETPPLi2 (or OisoBuTPPLi2) with SOCl2. The X-ray analysis and the characteristic UV-vis spectra of 1 and 3 revealed that these are the first examples of 16 pi nonaromatic porphyrins.     

A versatile method for preparation of O-alkylperoxycarbonic acids: epoxidation with alkyloxycarbonylimidazoles and hydrogen peroxide

A variety of O-alkylperoxycarbonic acids ($\text{2}$) were conveniently prepared $\text{in}$$\text{situ}$ by utilizing alkyloxycarbonylimidazoles ($\text{1}$) as their precursors. Epoxidation of alkenes with such peroxy-acids was studied and their reactivities were compared with those of peroxycarboxylic acids.     

Synthesis of a new PET/layered niobate hybrid material

A new organic/inorganic hybrid material was prepared by the polymerization of bis(hydroxyethyl) terephthalate (BHET) with a layered niobate compound, H₄Nb₆O₁₇, modified by 11-aminoundecanoic acid (AUA). The hybrid polymer films of BHET with H₄Nb₆O₁₇/AUA exhibited favorable characteristics, particularly of being optically clear, indicating the exfoliation and homogeneous dispersion of H₄Nb₆O₁₇ into the PET/niobate hybrid.     

Creation of highly functional thin films using electrochemical nanotechnology

This overview describes the results of our recent study of the application of electrochemical nanotechnology to the fabrication of magnetic recording materials, interconnects in ultra-large-scale integrated (ULSI) devices, energy storage materials, and on-chip biosensors. It is important to note that electrochemical processes play significant roles in developing and fabrication such sophisticated materials and devices. In the field of magnetic recording, electrodeposition methods for preparing CoNiFe and CoFe soft magnetic thin films with a high saturation magnetic flux density were newly developed, and the significant issues for obtaining those films are highlighted. In the area of ULSI interconnects, we developed a technique using a self-assembled monolayer (SAM) for direct bonding of the interconnect layer to SiO2, and proposed a novel electroless deposition method for fabricating a diffusion barrier layer. In the field of batteries, electrodeposited SnNi alloy was proposed as a future anode material for Li batteries, and electrochemical MEMS processes were shown to be useful for fabricating micro-sized direct methanol fuel cells (DMFCs) as portable batteries for electronics applications. In the area of chemical sensors, we developed a new process for fabricating field effect transistors (FETs) modified with SAMs for on-chip biosensing applications.     

A practical synthesis of (S)-2-cyclohexyl-2-phenylglycolic acid via organocatalytic asymmetric construction of a tetrasubstituted carbon center

[reaction: see text] A concise and enantioselective synthesis of (S)-2-cyclohexyl-2-phenylglycolic acid as a key intermediate for (S)-oxybutynin is reported. The crucial asymmetric tetrasubstituted carbon center was constructed with excellent stereoselectivity through the proline-catalyzed direct asymmetric aldol reaction between cyclohexanone and ethyl phenylglyoxylate under mild conditions.     

Microwave‐Assisted Palladium‐Catalyzed Direct Arylation of 1,4‐Disubstituted 1,2,3‐Triazoles with Aryl Chlorides

Treatment of 1,4‐disubstituted 1,2,3‐triazoles with aryl chlorides in the presence of potassium carbonate under palladium catalysis and microwave irradiation at 250 °C for 15 min leads to arylation of the triazole at the 5‐position. A variety of functional groups, including ester and hydroxy groups, are compatible. The procedure is suitable for the regioselective preparation of trisubstituted triazoles. Microwave irradiation accelerates the reaction, thus allowing the rapid synthesis of trisubstituted triazoles, which are difficult to synthesize selectively.     

Synthesis of Arenethiolate Complexes of Divalent and Trivalent Lanthanides from Metallic Lanthanides and Diaryl Disulfides: Crystal Structures of [{Yb(hmpa)(3)}(2)(&mgr;-SPh)(3)][SPh] and Ln(SPh)(3)(hmpa)(3) (Ln = Sm, Yb; hmpa = Hexamethylphosphoric Triamide)

A convenient and one-pot synthetic method of lanthanide thiolate compounds was developed. An excess of metallic samarium, europium, and ytterbium directly reacted with diaryl disulfides in THF to give selectively Ln(II) thiolate complexes, [Ln(SAr)(&mgr;-SAr)(thf)(3)](2) (1, Ln = Sm; 2, Ln = Eu; Ar = 2,4,6-triisopropylphenyl), Yb(SAr)(2)(py)(4) (3, py = pyridine), and [{Ln(hmpa)(3)}(2)(&mgr;-SPh)(3)][SPh] (6, Ln = Sm; 7, Ln = Eu; 8, Ln = Yb; hmpa = hexamethylphosphoric triamide). Reaction of metallic lanthanides with 3 equiv of disulfides afforded Ln(III) thiolate complexes, Ln(SAr)(3)(py)(n)()(thf)(3)(-)(n)() (9a, Ln = Sm, n = 3; 9b, Ln = Sm, n = 2; 10, Ln = Yb, n = 3) and Ln(SPh)(3)(hmpa)(3) (11, Ln = Sm; 12, Ln = Eu; 13, Ln = Yb). Thus, Ln(II) and Ln(III) thiolate complexes were prepared from the same source by controlling the stoichiometry of the reactants. X-ray analysis of 8 revealed that 8 has the first ionic structure composed of triply bridged dinuclear cation and benezenethiolate anion [8, orthorhombic, space group P2(1)2(1)2(1) with a = 21.057(9), b = 25.963(7), c = 16.442(8) ?, V = 8988(5) ?(3), Z = 4, R = 0.040, R(w) = 0.039 for 5848 reflections with I > 3sigma(I) and 865 parameters]. The monomeric structures of 11 and 13 were revealed by X-ray crystallographic studies [11, triclinic, space group P&onemacr; with a = 14.719(3), b = 17.989(2), c = 11.344(2) ?, alpha = 97.91(1), beta = 110.30(2), gamma = 78.40(1) degrees, V = 2751.9(9) ?(3), Z = 2, R = 0.045, R(w) = 0.041 for 7111 reflections with I > 3sigma(I) and 536 parameters; 13, triclinic, space group P&onemacr; with a = 14.565(2), b = 17.961(2), c = 11.302(1) ?, alpha = 97.72(1), beta = 110.49(1), gamma = 78.37(1) degrees, V = 2706.0(7) ?(3), Z = 2, R = 0.031, R(w) = 0.035 for 9837 reflections with I > 3sigma(I) and 536 parameters]. A comparison with the reported mononuclear and dinuclear lanthanide thiolate complexes has been made to indicate that the Ln-S bonds weakened by the coordination of HMPA to lanthanide metals have ionic character.