Yoshimitsu Tachi

NiII(TPA) as an efficient catalyst for alkane hydroxylation with m-CPBA

A simple Ni(II)(TPA) complex [TPA = tris(2-pyridylmethyl)amine] has been demonstrated to act as an efficient turnover catalyst for alkane hydroxylation with m-CPBA (m-chloroperbenzoic acid), in which contribution of a NiO(+) (nickel-oxo) type active oxygen species is suggested.

Biomimetic epoxide-opening cascades of oxasqualenoids triggered by hydrolysis of the terminal epoxide.

The biomimetic epoxide-opening cascades from squalene polyepoxides 4-6 to triterpene polyethers (oxasqualenoids) teurilene (1), glabrescol (2), and omaezakianol (3), respectively, were reproduced in a single event by chemical reaction. These cascades proceeded through the 5-exo tandem cyclization triggered by Brønsted acid-catalyzed hydrolysis of the terminal epoxide, mimicking the direct hydrolysis mechanism of epoxide hydrolases.

Ligand effects on NiII-catalysed alkane-hydroxylation with m-CPBA

Nickel(ii) complexes supported by a series of pyridylalkylamine ligands [tris(2-pyridylmethyl)amine (TPA; complexes and ), tris[2-(2-pyridyl)ethyl]amine (TEPA; complexes and ), 6-[N,N-bis(2-pyridylmethyl)aminomethyl]-2,4-di-tert-butylphenol ((Dtbp)Pym2H; complexes and ), 6-[N,N-bis[2-(2-pyridyl)ethyl]aminomethyl]-2,4-di-tert-butylphenol ((Dtbp)Pye2H; complexes and ), N-benzyl-bis(2-pyridylmethyl)amine ((Bz)Pym2; complex ) and N-benzyl-bis[2-(2-pyridyl)ethyl]amine ((Bz)Pye2; complex )] have been synthesized and structurally characterized by X-ray crystallographic analysis [coordinating counter anion (co-ligand) of complexes n (n = 1-6) is AcO(-) and that of complexes n (n = 1-4) is NO(3)(-)]. All complexes, except , were obtained as a mononuclear nickel(ii) complex exhibiting a distorted octahedral geometry, whereas complex was isolated as a dinuclear nickel(ii) complex bridged by two nitrate anions. Catalytic activity of the nickel(ii) complexes were examined in the oxidation of cyclohexane with m-CPBA as an oxidant. In all cases, the oxygenation reaction proceeded catalytically to give cyclohexanol as the major product together with cyclohexanone as the minor product. The complexes containing the pyridylmethylamine (Pym) metal-binding group (, , ) showed higher turnover number (TON) than those containing the pyridylethylamine (Pye) metal-binding group (, , ), whereas the alcohol/ketone (A/K) selectivity was much higher with the latter (Pye system) than the former (Pym system). On the other hand, the existence of the NO(3)(-) co-ligand (, and ) caused a lag phase in the early stage of the catalytic reaction. Electronic and steric effects of the supporting ligands as well as the chemical behavior of the co-ligands on the catalytic activity of the nickel(ii) complexes have been discussed on the basis of their X-ray structures.

Structure and photoluminescence property of two-dimensional coordination polymer complexes involving CuI6X6(X = Cl, Br, I) hexagon prism cluster supported by a tripodal tripyridine ligand with 1,3,5-triethylbenzene spacer

Treatment of cuprous halide (Cu(I)X, X = Cl, Br, and I) and a tripodal tripyridine ligand (L) consisting of a 1,3,5-triethylbenzene spacer gave a unique two-dimensional (2D) polymer sheet structure involving a rare Cu(I)(6)X(6) hexagon prism cluster unit, which exhibits intense fluorescence around 448-476 nm.

Total Synthesis of (−)-Lepadiformine A Utilizing Hg(OTf)2-Catalyzed Cycloisomerization Reaction

A cytotoxic marine alkaloid (-)-lepadiformine A (1) possesses a unique structure characterized by the trans-1-azadecalin AB ring system fused with the AC spiro-cyclic ring. In this research, we found that a cycloisomerization reaction from amino ynone 2 to a 1-azaspiro[4.5]decane skeleton 3, corresponding to the AC ring system of 1, is promoted by Hg(OTf)(2). Thus, we have accomplished the efficient total synthesis of (-)-lepadiformine A in 28% overall yield by featuring the novel Hg(OTf)(2)-catalyzed cycloisomerization.

Structure and O2-reactivity of copper(I) complexes supported by pyridylalkylamine ligands

The structure and O2-reactivity of a series of copper(I) complexes supported by the pyridylalkylamine ligands are summarized, and the ligand effects such as the chelate ring size effect (five- vs. six-membered ring), the denticity effect (tetradentate vs. tridentate vs. didentate), the steric effect of 6-methylpyridine and the steric and/or electronic effects of N-alkyl substituents are discussed in detail.

Diastereoselective synthesis of the indeno-tetrahydropyridine core bearing a diaryl-substituted stereogenic quaternary carbon center of haouamine B

The characteristic indeno-tetrahydropyridine core of cytotoxic haouamine B (2) was efficiently synthesized featuring the diastereoselective construction of a diaryl-substituted stereogenic quaternary center by an intramolecular Pd-catalyzed α-C-arylation and subsequent direct conversion of the vinylogous imide function into the C2-C25 double bond by TsNHNH(2).

Formation and spectroscopic characterization of the dioxygen adduct of a heme?Cu complex possessing a cross-linked tyrosine?histidine mimic: modeling the active site of cytochrome c oxidaseElectronic supplementary information (ESI) available: experiment procedures for preparing metal porphyrins and oxygenation reaction. See http://www.rsc.org/suppdata/cc/b3/b311538k/

A binucleating porphyrin with covalently appended copper chelates having a cross-linked imidazole-phenol group as the novel active site model of cytochrome c oxidase has been prepared, and the dioxygen adduct of its iron(II)-copper(I) complex was spectroscopically characterized.

Ligand-binding Ability of a Porphyrin Core in a Dendrimer with Rigid Branched Terminal Components

A dendrimer with rigid branched terminal components was prepared by a copper-catalyzed Hüisgen 1,3-dipolar cycloaddition reaction. A zinc 5,15-diethynyl-10,20-bis(3,5-di- tert-butylphenyl)porphyrin unit was incorporated at the core of the dendrimer as a receptor site for an added pyridyl ligand. The appearance of an absorption band characteristic of the planar conformer of conjugated chains in the terminal components suggested that the dendrimer adopts a folded higher order structure in dichloromethane at 25 °C. The binding constant between the zinc porphyrin core and a pyridyl ligand was evaluated by means of UV-vis absorption titration and compared with that of a suitable reference compound. The incorporation of the zinc porphyrin core into the folded dendrimer led to considerable suppression of its ligand-binding ability.