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2006, Vol. 35 No. 1-12
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Dec. 2006, Vol.35 No.12
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Web Release Date:
October 28, 2006
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| 1320 |
Transition Metal-catalyzed Carbochalcogenation of Alkynes |
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Hitoshi Kuniyasu and Nobuaki Kambe |
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The progress of transition metal-catalyzed carbochalcogenation of alkynes, which can be performed by using readily available catalysts, is reviewed. It has been proposed that stereo- and regioselective insertion of alkynes into the metal complexes is involved in the catalytic cycles. These reactions clearly demonstrate the synthetic versatility of organochalcogen compounds in transition metal-catalyzed reactions. |
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Nov. 2006, Vol.35 No.11
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Web Release Date:
September 30, 2006
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| 1204 |
Recent Development of 6π-Electrocyclic Photochromic Systems |
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Kenji Matsuda and Masahiro Irie |
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Photochromic compounds are currently recognized as the promising candidates for future optoelectronics, such as memories and switches. Photochemical pericyclic reactions between 1,3,5-hexatriene and 1,3-cyclohexadiene have been used in several ways to construct versatile photochromic compounds. Recent development of 6π-electrocyclic photochromic systems is overviewed. |
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Oct. 2006, Vol.35 No.10
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Web Release Date:
August 29, 2006
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| 1082 |
Cycloaddition Reactions of Transition Metal-containing Benzopyrylium and Related Zwitterionic Intermediates |
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Hiroyuki Kusama and Nobuharu Iwasawa |
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Recent advances in generation and cycloaddition reactions of transition metal-containing benzopyrylium and related zwitterionic intermediates from o-alkynylphenylcarbonyl or imine derivatives are summarized focussing on the difference of the two reaction pathways, that is, [3 + 2] and [4 + 2] cycloaddition reactions. |
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Sep. 2006, Vol.35 No.9
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Web Release Date:
July 29, 2006
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| 978 |
From Industrial Colorants to Single Photon Sources and Biolabels: The Fascination and Function of Rylene Dyes |
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Andreas Herrmann and Klaus Müllen |
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Perylene dyes are key chromophores in dyestuff chemistry. In this review, their chemical modifications and the generation of new rylene chromophores are discussed. Special attention will be paid to applications of rylene dyes. These range from innovative solutions for classical coloration to their use for high-tech purposes like laser marking, single molecule spectroscopy, or organic electronic devices. |
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| Aug. 2006, Vol.35 No.8
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Web Release Date:
June 27, 2006
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| 824 |
The Tishchenko Reaction: A Classic and Practical Tool for Ester Synthesis |
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Tsunetake Seki, Tetsuo Nakajo, and Makoto Onaka |
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The Tishchenko reaction is surveyed on the reaction mechanisms, homogeneous and heterogeneous catalysts developed for the reaction, a number of specific examples, and the utility of the reaction in industrially large-scale production of ethyl acetate from acetaldehyde. |
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| Jul. 2006, Vol.35 No.7
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Web Release Date:
June 3, 2006
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| 694 |
Bio-inspired Programmable Self-assembly on DNA Templates |
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Kentaro Tanaka and Mitsuhiko Shionoya |
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Besides the biological importance of DNA as storage of genetic information, DNA is a smart molecule to assemble functional units since it is possible to use sequences of nucleobases to encode molecularly assembled systems in a predetermined fashion over a wide range in size. This review highlights recent advance in precise control of molecular assembly on DNA templates directed towards functionalized materials. |
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| Jul. 2006, Vol.35 No.7
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Web Release Date:
May 30, 2006
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| 688 |
Structures and Sorption Properties of Ionic Crystals of Polyoxometalates with Macrocation |
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Noritaka Mizuno and Sayaka Uchida |
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Polyoxometalates are nanosized metal–oxygen macroanions and suitable building blocks of ionic crystals with nano-structures in combination with appropriate macrocations. In this review, (1) formation of ionic crystals by the complexation of the polyoxometalates with a macrocation and the hydrophilic guest sorption properties, (2) effects of charges of polyoxometalates on the structures and sorption properties of ionic crystals, and (3) construction of both hydrophilic and hydrophobic channels in the crystal lattice of the polyoxometalate-based ionic crystals are highlighted. |
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| Jun. 2006, Vol.35 No.6
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Web Release Date:
April 29, 2006
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| 552 |
Stereoselective C-Alkynylation, Allenylation, and Prop-2-ynylation Leading to Sugar Glycosides |
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Rungnapha Saeeng and Minoru Isobe |
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Carbohydrates have been recognized and utilized for a long time as the starting materials for target-oriented syntheses toward optically active compounds. C-Glycosides are often employed for this purpose because they have much potential for the introduction of new stereogenic centers to the side chain. We describe herein various methods for the introduction of carbon chains to the sugar rings under acidic condition, particularly in the form of alkynyl, allenyl, or prop-2-ynyl group at the anomeric position with high stereoselectivity. |
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| May 2006, Vol.35 No.5
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Web Release Date:
April 1, 2006
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| 468 |
Propylene Oxide Synthesis and Selective Oxidation over Supported Metal Oxide Photocatalysts with Molecular Oxygen |
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Fumiaki Amano and Tsunehiro Tanaka |
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Recent progress of photocatalytic epoxidation of propylene with molecular oxygen is reviewed. Highly dispersed metal oxide photocatalysts, such as silica-supported V2O5, Nb2O5, and TiO2 with low loading, promote steady-state propylene oxide formation with high selectivity (>40%). The isolated tetrahedrally-coordinated species in the ligand-to-metal charge-transferred state is the photocatalytic active site. The photo-induced hole center localized on the lattice oxygen plays a significant role for the photocatalytic epoxidation. The key step in the selective photocatalytic oxidation over isolated VO4 tetrahedra is the electron transfer from a hydrocarbon to the photo-induced hole center. The lattice oxygen is inserted in the photogenerated products. |
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| Apr. 2006, Vol.35 No.4
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Web Release Date:
March 11, 2006
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| 342
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Localization of Electromagnetic Wave in 3D Periodic and Fractal Structures
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Yoshinari Miyamoto, Soshu Kirihara, and Mitsuo Wada Takeda
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Localization or confinement of electromagnetic or optical waves is reviewed briefly in respect to the wave interaction with the specific structures of periodic, random, and fractal (self-similar) geometries, which can enhance strong interference, scattering, and resonance of waves. The localization of microwave in photonic crystals with diamond structure and in photonic fractals with Menger sponge structure of dielectric media is reported and discussed about the difference of localization behaviors. These 3D structures are fabricated easily from liquid photosensitive resins or ceramic dispersed ones by a CAD/CAM stereolithography. The localization in photonic fractals is supported with several measurements of transmission, 90° wave scattering, electric field intensity profile, and FDTD (finite-difference time-domain) simulation for localized modes. An empirical equation to predict the localization frequencies shows good agreements with measured results as well. The localization in a photonic crystal can be explained by Bragg scattering, while that in a photonic fractal by resonance in the fractal cavity.
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| Mar. 2006, Vol.35 No.3
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Web Release Date:
January 28, 2006
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| 242
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Recent Development of Multireference Density Functional Theory
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Shusuke Yamanaka, Kazuto Nakata, Toshikazu Takada, Koichi Kusakabe, Jesus M. Ugalde, and Kizashi Yamaguchi
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We review a recently developed ab initio multireference (MR)-density functional theory (DFT) approach based on the partially interacting reference systems. Instead of Kohn–Sham equations, we introduce the auxiliary CI equation with the effective DFT potential field. For practice, we classify electrons of the target system into valence electrons and other electrons. The former plays the quantum resonating feature of electronic structure of molecular species, while the latter affects the electronic properties via the effective correlation potential for the former electrons. The theoretical devices in our MR-DFT are introduced to avoid the double counting problem for any combination of a wavefunction and a correlation functional. Some numerical examples are presented.
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| Feb. 2006, Vol.35 No.2
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Web Release Date:
December 28, 2005
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| 148
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Chiral Symmetry Breaking in Chiral Crystallization and Soai Autocatalytic Reaction
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Ilya D. Gridnev
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Complete chiral crystallization and absolute chiral synthesis are both fascinating phenomena shedding light on the possible origins of homochirality in Nature and opening perspectives for efficient preparations of optically pure materials. Originally, these two phenomena have been considered mechanistically quite different belonging to the hetero- and homogeneous systems, respectively. However, the results of the active research in both fields undertaken in the last few years suggest that there may be a much closer likeness of the most important mechanistic features of these two phenomena. The present review brings together the latest data on the complete chiral crystallization and absolute chiral synthesis including our own data on the mechanism and spontaneous break of chirality in the Soai asymmetric autocatalysis.
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| Feb. 2006, Vol.35 No.2
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Web Release Date:
December 27, 2005
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| 142
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Heterolytic Dissociation of C–H Bond of Methane over Ag+-exchanged Zeolites and Conversion of Methane into Higher Hydrocarbons in the Presence of Ethene or Benzene
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Toshihide Baba and Koji Inazu
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Formation of highly polarized methoxy groups (ZOδ−CH3δ+) and silver hydride species (Agn–H) over Ag+-exchanged zeolites and reaction of the CH3δ + with ethene and benzene form propene and toluene, respectively.
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| Jan. 2006, Vol.35 No.1
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Web Release Date:
November 29, 2005
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Preparation and Reactions of Heteroaryl Organomagnesium Compounds
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Hiriyakkanavar Ila, Oliver Baron, Andreas J. Wagner, and Paul Knochel
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The halogen/magnesium-exchange reaction has opened new perspectives in organic synthesis and has considerably extended the range of available functionalized aryl and heteroaryl magnesium compounds bearing functional groups such as ester, nitrile, iodide, imine, or even sensitive groups like nitro, hydroxy, and boronic esters. The present review summarizes the applications of these functionalized heteroaryl- and arylmagnesium compounds for the synthesis of a wide variety of regiospecifically functionalized five- and six-membered heterocycles.
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