Bulletin of the Chemical Society of Japan

Vol. 73, No. 09 (September, 2000)

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Copyright (C) 2000 by The Chemical Society of Japan


CONTENTS


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Accounts
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Synthetic Incorporation of Metal Complexes into Nucleic Acids and Peptides Directed toward Functionalized Molecules

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Mitsuhiko Shionoya* and Kentaro Tanaka

pages 1945-1954



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Articles
Orgainc and Biological
=============================

Classification and Prediction of Reagents' Roles by FRAU System with Self-Organizing Neural Network Model

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Hiroko Satoh,*, Kimito Funatsu, Keiko Takano, and Tadashi Nakata

pages 1955-1965



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Articles
General and Physical
=============================

Hydration Structure of Glycine Molecules in Aqueous Alkaline Solutions

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Kentaro Sugawara, Yasuo Kameda,* Takeshi Usuki, Osamu Uemura, and Toshiharu Fukunaga

pages 1967-1972


Production of Negative Ions from Fluorocarbons and Reaction Mechanism

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Seiko Nakagawa* and Toshinari Shimokawa*

pages 1973-1978


Chiral Replacement Criterion for Characterizing Holotopic and Hemitopic Relationships

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Shinsaku Fujita

pages 1979-1986


Heat Capacities of Isomeric 2-Butoxyethanols from 13 to 300 K: Fusion and Glass Transition

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Tooru Atake,* Hitoshi Kawaji, Takeo Tojo, Koji Kawasaki, Yasushiro Ootsuka, Maki Katou, and Yoshikata Koga

pages 1987-1991


Self-Assembled Monolayers of Heme Derivatives on a Gold Surface

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Kazutoshi Kobayashi,*, Shin'ichiro Imabayashi, Katsuhiko Fujita, Kazuhide Nonaka, Takashi Kakiuchi,, Hiroyuki Sasabe, and Wolfgang Knoll

pages 1993-2000


In-Bond Orbitals: A Comprehensive Graphical Expression of Orbital Interaction

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Hiroshi Ichikawa,* Hirotaka Kagawa, and Chikara Kaneko

pages 2001-2008


Characterization of Prochirality and Classification of Meso -Compounds by Means of the Concept of Size-Invariant Subductions

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Shinsaku Fujita

pages 2009-2016


Site-Selective X-Ray Absorption Fine Structure (XAFS) Spectroscopy. (1) Design of Fluorescence Spectrometer and Emission Spectra

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Yasuo Izumi,* Hiroyuki Oyanagi, and Hiroyasu Nagamori

pages 2017-2023



=============================
Articles
Analitical and Inorganic
=============================

Reinvestigation of Decarboxylation Kinetics from the Hydrogencarbonatocobalt(III) Intermediate

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Yoichi Kitamura,* Leona Yano, Kazuya Fujimori, Ryuji Mizuki, Masayuki Hayashi, and Akira Shibata

pages 2025-2032


NMR Studies on the Aggregation of Mononuclear and Dinuclear Cobalt(III) Amphiphilic Complexes Having Alkyl Chains

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Masayasu Iida,* Akie Sakamoto, Taeko Yamashita, Kaori Shundoh, Shiho Ohkawa, and Kazuaki Yamanari

pages 2033-2041


Circular Dichroism Spectrophotometric Determination of Metal Ions Using Optically Active Tris(thiolato) Type Rhodium(III) Complexes

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Sen-ichi Aizawa,*, Yasushi Sone, Siti Khajar, Yuuki Ohishi, Shinkichi Yamada, and Motoshi Nakamura

pages 2043-2050


[Ru(bpy)2 (dppz-NH2 )]2+ Complex (dppz-NH2 : 7-Amino-dipyrido[3,2- a : 2' ,3' - c ]phenazine) as a Useful Photosensitizing Unit for the Construction of Photoinduced Energy Transfer Systems

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Chang-Shik Choi, Lallan Mishra, Toshiki Mutai, and Koji Araki*

pages 2051-2058


Magnetic Properties of Iron(III) Complexes with Photoisomerizable Ligands

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Shigeyuki Hirose, Shinya Hayami, and Yonezo Maeda*

pages 2059-2066


Syntheses, Crystal Structures, and Some Spectrochemical Properties of S-Bridged Tetranuclear Complexes with Stacking Arrangements Composed of Planar Palladium(II) Units

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Yasunori Yamada,* Kiyoshi Fujisawa, and Ken-ichi Okamoto*

pages 2067-2073



=============================
Articles
Orgainc and Biological
=============================

Enantioselective Photocyclization of Acrylanilides and N -Ethyl- N -methylbenzoylformamide in Inclusion Crystals with ( R , R )-(-)-[ trans ]-2,3-Bis( -hydroxydiphenylmethyl)-1,4-dioxaspiro-[4.4]nonane and -[4.5]decane. Mechanistic Study Based on X-Ray Crystal Structure Analyses

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Shigeru Ohba,* Hiroyuki Hosomi, Koichi Tanaka, Hisakazu Miyamoto, and Fumio Toda,*,

pages 2075-2085


A Novel Maleic Anhydride Derivative from the Fungus Talaromyces sp. No. 10092

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Ryo Yamanishi, Kazuki Okada, Norihusa Tamugi, Makoto Iwashima, and Kazuo Iguchi*,

pages 2087-2091


Synthesis, Structure, and Reactions of Octakis(1,1,2-trimethylpropyl)octagermacubane

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Masafumi Unno, Koichi Higuchi, Koji Furuya, Hiroaki Shioyama, Soichiro Kyushin, Midori Goto, and Hideyuki Matsumoto*

pages 2093-2097


An NMR Study on the Ruthenium Complex-Catalyzed C-H/Olefin Coupling Reaction

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Katsuma Hiraki,*, Takayuki Ishimoto, and Hiroyuki Kawano

pages 2099-2108


Synthesis, Structure, and Properties of Hexaaryl[3]radialenes

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Tetsuya Enomoto, Naoki Nishigaki, Hiroyuki Kurata, Takeshi Kawase, and Masaji Oda*

pages 2109-2114


The Juli-Colonna Asymmetric Epoxidation Reaction of Chalcone Catalyzed by Length Defined Oligo- L -leucine: Importance of the N -Terminal Functional Group and Helical Structure of the Catalyst in the Asymmetric Induction

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Ryukichi Takagi, Toshiki Manabe, Akiko Shiraki, Arata Yoneshige, Yoshikazu Hiraga, Satoshi Kojima, and Katsuo Ohkata*

pages 2115-2121


Lattice Inclusion Complexation in Water. Hydrogen Bonding in Selective Guest Binding and Catalysis

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Takehisa Dewa, Toshiyuki Saiki, Yuki Imai, 1) Ken Endo, and Yasuhiro Aoyama*

pages 2123-2127


Synthesis and Reduction of Silyl-Substituted [5]Radialene. Characterization and Structure of a [5]Radialene Tetraanion with a Ten-Center, Fourteen-Electron -System

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Tsukasa Matsuo, Hidetoshi Fure, and Akira Sekiguchi*

pages 2129-2137


Reaction of Trialkyl(dibromomethyl)silanes or 1,2-Bis(dibromomethyl)benzene with Triorganomanganates. A Facile and Selective Synthesis of Alkenylsilanes and 1,2-Diaryl-1,2-dihydrobenzocyclobutenes

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Hirotada Kakiya, Hiroshi Shinokubo, and Koichiro Oshima*

pages 2139-2147


Palladium(II)-Catalyzed Michael-Type Addition Reactions Using Aryltin Compounds

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Toshiyuki Ohe, Takeshi Wakita, Shin-ichi Motofusa, Chan Sik Cho, Kouichi Ohe, and Sakae Uemura*

pages 2149-2155


Separation of Orientational Disorder in the X-Ray Analysis of the Kinetically Stabilized 2-Silanaphthalene

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Keiji Wakita, Norihiro Tokitoh,*,, and Renji Okazaki,

pages 2157-2158


Trialkylmanganate Mediated Radical Addition of Triphenylgermane to Carbon-Carbon Multiple Bonds

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Hidenori Kinoshita, Hirotada Kakiya, and Koichiro Oshima*

pages 2159-2160



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Articles
Applied and Materials
=============================

A Universal Structural Model for Human Hair to Understand the Physical Properties 1

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Shinobu Nagase, Masato Ohshika, Shinya Ueda, Naoki Satoh, and Kaoru Tsujii*,

pages 2161-2167


A Universal Structural Model for Human Hair to Understand the Physical Properties 2. Mechanical and Permeation Behaviors

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Masahiko Sakai, Shinobu Nagase, Tomoyuki Okada, Naoki Satoh, and Kaoru Tsujii*,

pages 2169-2177



Bulletin of the Chemical Society of Japan [Graphical Abstracts]

Bulletin of the Chemical Society of Japan

Vol. 73, No. 09 (September, 2000)

Go to the Full Text PDF

Copyright (C) 2000 The Chemical Society of Japan


GRAPHICAL ABSTRACTS


=============================
Accounts
=============================


Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 1945-1954 (2000) [Vol. 73, No. 9, September, 2000]

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Synthetic Incorporation of Metal Complexes into Nucleic Acids and Peptides Directed toward Functionalized Molecules

Mitsuhiko Shionoya* and Kentaro Tanaka


Illustration

As novel synthetic incorporation of metal complexes into DNA and peptides, first, artificial -C -nucleosides bearing a chelator nucleobase have been synthesized for alternative metal-assisted base pairing. Secondly, the liquid-phase synthesis of cyclic metallopeptides, cyclo [-Gly- L -Cys(terpyPtII )-]n Cln (n = 3 , 4), has been exploited.

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=============================
Articles
Orgainc and Biological
=============================


Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 1955-1965 (2000) [Vol. 73, No. 9, September, 2000]

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Classification and Prediction of Reagents' Roles by FRAU System with Self-Organizing Neural Network Model

Hiroko Satoh,*, Kimito Funatsu, Keiko Takano, and Tadashi Nakata


Illustration

A classification and prediction method of reagents' roles is presented. The same dimensional factors characterize reagents independent of the number of atoms. A neural network that was improved for this study successfully classified the reagents and produced a reagent-roles correlation model.

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=============================
Articles
General and Physical
=============================


Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 1967-1972 (2000) [Vol. 73, No. 9, September, 2000]

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Hydration Structure of Glycine Molecules in Aqueous Alkaline Solutions

Kentaro Sugawara, Yasuo Kameda,* Takeshi Usuki, Osamu Uemura, and Toshiharu Fukunaga


Illustration

Neutron diffraction with 14 N/15 N and H/D isotopic substitution method has been applied to aqueous 2 mol% glycine solutions under high-pH condition. Detailed structural information on the first hydration shell around both amino- and methylene groups of the glycine molecule is derived.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 1973-1978 (2000) [Vol. 73, No. 9, September, 2000]

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Production of Negative Ions from Fluorocarbons and Reaction Mechanism

Seiko Nakagawa* and Toshinari Shimokawa*


Illustration

The temperature dependence of negative ions from C5 F5 N and C6 F5 X (X = F , CN, CF3 , C6 F5 ) was studied by using negative chemical ionization mass spectrometry. The results of geometry calculation have shown that production and reaction mechanism of negative ions are almost the same.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 1979-1986 (2000) [Vol. 73, No. 9, September, 2000]

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Chiral Replacement Criterion for Characterizing Holotopic and Hemitopic Relationships

Shinsaku Fujita


Illustration

A chiral replacement criterion has been proposed to characterize stereochemical equivalence such as holotopic and hemitopic relationships.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 1987-1991 (2000) [Vol. 73, No. 9, September, 2000]

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Heat Capacities of Isomeric 2-Butoxyethanols from 13 to 300 K: Fusion and Glass Transition

Tooru Atake,* Hitoshi Kawaji, Takeo Tojo, Koji Kawasaki, Yasushiro Ootsuka, Maki Katou, and Yoshikata Koga


Illustration

We measured the heat capacities of the three isomers of 2-Butoxyethanol from 13 to 300 K by adiabatic calorimetry, as well as the density of the liquid and supercooled liquid states. The thermodynamic functions, including the amplitude of entropy fluctuation, were determined.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 1993-2000 (2000) [Vol. 73, No. 9, September, 2000]

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Self-Assembled Monolayers of Heme Derivatives on a Gold Surface

Kazutoshi Kobayashi,*, Shin'ichiro Imabayashi, Katsuhiko Fujita, Kazuhide Nonaka, Takashi Kakiuchi,, Hiroyuki Sasabe, and Wolfgang Knoll


Illustration

The adsorption behavior of native heme and its thiolated derivatives on gold surfaces was demonstrated using SPS, IR, and UV spectroscopies. Their redox behavior was also characterized using CV and ER methods.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2001-2008 (2000) [Vol. 73, No. 9, September, 2000]

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In-Bond Orbitals: A Comprehensive Graphical Expression of Orbital Interaction

Hiroshi Ichikawa,* Hirotaka Kagawa, and Chikara Kaneko


Illustration

The authors propose ``in-bond orbitals'' to compensate the shortcomings of minimal LCAO picture without destroying its simple concept. In-bond orbitals express well the electronic structures of bonding and antibonding internuclear regions. Furthermore, they are continuously correlated with the AOs of the united atom.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2009-2016 (2000) [Vol. 73, No. 9, September, 2000]

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Characterization of Prochirality and Classification of Meso -Compounds by Means of the Concept of Size-Invariant Subductions

Shinsaku Fujita


Illustration

The concept of size-invariant subductions has been proposed to design prochiral molecules. Thereby, prochiral molecules having chiral ligands are classified into extrinsic and intrinsic meso compounds.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2017-2023 (2000) [Vol. 73, No. 9, September, 2000]

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Site-Selective X-Ray Absorption Fine Structure (XAFS) Spectroscopy. (1) Design of Fluorescence Spectrometer and Emission Spectra

Yasuo Izumi,* Hiroyuki Oyanagi, and Hiroyasu Nagamori


Illustration

A Rowland fluorescence spectrometer equipped with bent Ge(111) crystal and scintillation counter was developed for site-selective XAFS. Chemical shifts of Cu K and Cr K peaks were measured. Energy resolution was determined by three slit sizes in the spectrometer.

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=============================
Articles
Analitical and Inorganic
=============================


Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2025-2032 (2000) [Vol. 73, No. 9, September, 2000]

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Reinvestigation of Decarboxylation Kinetics from the Hydrogencarbonatocobalt(III) Intermediate

Yoichi Kitamura,* Leona Yano, Kazuya Fujimori, Ryuji Mizuki, Masayuki Hayashi, and Akira Shibata


Illustration

The title reaction velocity depends on the acidity of the solution. The amphiproticity of the hydrogencarbonatocobalt(III) intermediate is derived therefrom: Ka = 10-6 -0.6 M and Kb/Kw 0.3 M-1 .

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2033-2041 (2000) [Vol. 73, No. 9, September, 2000]

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NMR Studies on the Aggregation of Mononuclear and Dinuclear Cobalt(III) Amphiphilic Complexes Having Alkyl Chains

Masayasu Iida,* Akie Sakamoto, Taeko Yamashita, Kaori Shundoh, Shiho Ohkawa, and Kazuaki Yamanari


Illustration

The aggregation of novel-type cobalt(III) surfactants, such as [Co(en)2 {NH2 (CH2 )2 S(1-Cn H2n+1 )}]3+ (n = 6 , 8, and 12) and [(en)2 Co{NH2 (CH2 )2 S(CH2 )m S(CH2 )2 NH2 }Co(en)2 ]6+ (m = 8 and 12), was studied in water using multinuclear NMR spectroscopies, 1 H NMR self-diffusions, and 1 H NMR chemical shifts. The 59 Co linewidths and 35 Cl relaxation rates show cmcs for premicelles in the hexyl mononuclear and octyl dinuclear complex systems.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2043-2050 (2000) [Vol. 73, No. 9, September, 2000]

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Circular Dichroism Spectrophotometric Determination of Metal Ions Using Optically Active Tris(thiolato) Type Rhodium(III) Complexes

Sen-ichi Aizawa,*, Yasushi Sone, Siti Khajar, Yuuki Ohishi, Shinkichi Yamada, and Motoshi Nakamura


Illustration

Circular dichroism (CD) spectrophotometric determinations of Fe(III), Fe(II), Co(III), Co(II), and Ni(II) have been successful by taking advantage of the S -bridged trinuclear complex formation of fac (S )-[Rh(aet or L -cys-N ,S )3 ]0 or 3- . This method is quite simple and effective for the simultaneous determination of metal ions.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2051-2058 (2000) [Vol. 73, No. 9, September, 2000]

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[Ru(bpy)2 (dppz-NH2 )]2+ Complex (dppz-NH2 : 7-Amino-dipyrido[3,2- a : 2' ,3' - c ]phenazine) as a Useful Photosensitizing Unit for the Construction of Photoinduced Energy Transfer Systems

Chang-Shik Choi, Lallan Mishra, Toshiki Mutai, and Koji Araki*


Illustration

Photoinduced energy-transfer systems were conveniently constructed by reacting a novel building block, [Ru(bpy)2 (dppz-NH2 )]2+ , with energy-accepting units having a carboxylic acid function.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2059-2066 (2000) [Vol. 73, No. 9, September, 2000]

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Magnetic Properties of Iron(III) Complexes with Photoisomerizable Ligands

Shigeyuki Hirose, Shinya Hayami, and Yonezo Maeda*


Illustration

New Iron(III) complexes [Fe(salten)(trans -stpy)]BPh4 .acetone.0.5H2 O 1 and [Fe(salten)(cis -stpy)]BPh4 2 with cis -trans photoisomerizable ligands, 4-styrylpyridine exhibit spin-crossover phenomena in a solid and in an acetonitrile solution. Light irradiation to 1 brings about isomerization from trans - to cis - of 4-styrylpyridine.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2067-2073 (2000) [Vol. 73, No. 9, September, 2000]

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Syntheses, Crystal Structures, and Some Spectrochemical Properties of S-Bridged Tetranuclear Complexes with Stacking Arrangements Composed of Planar Palladium(II) Units

Yasunori Yamada,* Kiyoshi Fujisawa, and Ken-ichi Okamoto*


Illustration

The reaction of [Pd(aet)2 ] (aet = 2 -aminoethanethiolate) with [Pd(NO3 )2 (diimine)] (diimine = 2 ,2' -bipyridine (bpy), 4,4' -dimethyl-2,2' -bipyridine (dmbpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dmphen)) gave S-bridged tetranuclear complexes [{Pd(diimine)}2 {Pd(aet)2 }2 ]4+ . Some spectrochemical properties of these complexes are discussed in relation to their crystal structures, which were determined by X-ray structural analysis.

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=============================
Articles
Orgainc and Biological
=============================


Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2075-2085 (2000) [Vol. 73, No. 9, September, 2000]

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Enantioselective Photocyclization of Acrylanilides and N -Ethyl- N -methylbenzoylformamide in Inclusion Crystals with ( R , R )-(-)-[ trans ]-2,3-Bis( -hydroxydiphenylmethyl)-1,4-dioxaspiro-[4.4]nonane and -[4.5]decane. Mechanistic Study Based on X-Ray Crystal Structure Analyses

Shigeru Ohba,* Hiroyuki Hosomi, Koichi Tanaka, Hisakazu Miyamoto, and Fumio Toda,*,


Illustration

The absolute configurations of the photoproducts of guests are dependent on the hosts. The structures of the inclusion crystals have been determined to elucidate the mechanism of the enantioselectivities in the solid-state reaction.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2087-2091 (2000) [Vol. 73, No. 9, September, 2000]

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A Novel Maleic Anhydride Derivative from the Fungus Talaromyces sp. No. 10092

Ryo Yamanishi, Kazuki Okada, Norihusa Tamugi, Makoto Iwashima, and Kazuo Iguchi*,


Illustration

A new maleic anhydride derivative 1 (FR222398) was isolated from fermentations with the fungus Talaromyces sp. No. 10092. The structure of 1 was determined based on spectroscopic analysis and chemical conversion. The sodium salt of 1 showed a dispersant activity toward kaolin suspension.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2093-2097 (2000) [Vol. 73, No. 9, September, 2000]

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Synthesis, Structure, and Reactions of Octakis(1,1,2-trimethylpropyl)octagermacubane

Masafumi Unno, Koichi Higuchi, Koji Furuya, Hiroaki Shioyama, Soichiro Kyushin, Midori Goto, and Hideyuki Matsumoto*


Illustration

Octakis(1,1,2-trimethylpropyl)octagermacubane ( 1 ) was synthesized by the condensation reaction, and characterized by X-ray crystallography. The ring-opening reaction followed by skeletal rearrangement of 1 took place to give endo ,exo - and exo ,exo -4,8-dichlorooctathexyltetracyclo[3.3.0.02,7 .03,6 ]octagermanes. Treatment of these dichlorides with sodium afforded octagermacubane 1 .

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2099-2108 (2000) [Vol. 73, No. 9, September, 2000]

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An NMR Study on the Ruthenium Complex-Catalyzed C-H/Olefin Coupling Reaction

Katsuma Hiraki,*, Takayuki Ishimoto, and Hiroyuki Kawano


Illustration

An NMR spectroscopy for reactions among [RuH2 (CO)(PPh3 )3 ], styrene, and 3' -(trifluoromethyl)acetophenone detects three cyclometallated hydridoruthenium (II) complexes, 8 , 9 , and 12 . On the basis of these data, a mechanism for the ruthenium complex-catalyzed C-H/olefin coupling reaction is proposed.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2109-2114 (2000) [Vol. 73, No. 9, September, 2000]

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Synthesis, Structure, and Properties of Hexaaryl[3]radialenes

Tetsuya Enomoto, Naoki Nishigaki, Hiroyuki Kurata, Takeshi Kawase, and Masaji Oda*


Illustration

Hexaphenyl[3]radialene and its derivatives here first synthesized are stable, orange to red, crystalline substances. Among them hexa-p -nitro derivative has a strong electron affinity and X-ray analysis of hexa-p -cyano derivative shows a double three-bladed propeller conformation.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2115-2121 (2000) [Vol. 73, No. 9, September, 2000]

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The Juli-Colonna Asymmetric Epoxidation Reaction of Chalcone Catalyzed by Length Defined Oligo- L -leucine: Importance of the N -Terminal Functional Group and Helical Structure of the Catalyst in the Asymmetric Induction

Ryukichi Takagi, Toshiki Manabe, Akiko Shiraki, Arata Yoneshige, Yoshikazu Hiraga, Satoshi Kojima, and Katsuo Ohkata*


Illustration

Juli-Colonna asymmetric epoxidation using oligo- L -leucine with defined degrees of polymerization was investigated. The presence of an unprotected amine moiety at the N -terminus played an important role for high asymmetric induction.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2123-2127 (2000) [Vol. 73, No. 9, September, 2000]

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Lattice Inclusion Complexation in Water. Hydrogen Bonding in Selective Guest Binding and Catalysis

Takehisa Dewa, Toshiyuki Saiki, Yuki Imai, 1) Ken Endo, and Yasuhiro Aoyama*


Illustration

A hydrogen-bonded network solid, anthracenebisresorcinol (host 1 ), selectively incorporates two mols of polar guests from an aqueous solution via cooperation of hydrogen bonding and apolar interactions. Host 1 also catalyzes the Diels-Alder reaction of acrylaldehyde with 1,3-cyclohexadiene.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2129-2137 (2000) [Vol. 73, No. 9, September, 2000]

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Synthesis and Reduction of Silyl-Substituted [5]Radialene. Characterization and Structure of a [5]Radialene Tetraanion with a Ten-Center, Fourteen-Electron -System

Tsukasa Matsuo, Hidetoshi Fure, and Akira Sekiguchi*


Illustration

The silyl-substituted [5]radialene 2 was reacted with lithium metal in tetrahydrofuran to give dark red crystals of the tetralithium salt 4 of [5]radialene.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2139-2147 (2000) [Vol. 73, No. 9, September, 2000]

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Reaction of Trialkyl(dibromomethyl)silanes or 1,2-Bis(dibromomethyl)benzene with Triorganomanganates. A Facile and Selective Synthesis of Alkenylsilanes and 1,2-Diaryl-1,2-dihydrobenzocyclobutenes

Hirotada Kakiya, Hiroshi Shinokubo, and Koichiro Oshima*


Illustration

Treatment of trialkyl(dibromomethyl)silanes with trialkylmanganate provided (E )-1-trialkylsilyl-1-alkenes with high stereoselectivity in good yields. The reaction of 1,2-bis(dibromomethyl)benzene with triphenylmanganate gave 1,2-diphenyl-1,2-dihydrobenzocyclobutene.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2149-2155 (2000) [Vol. 73, No. 9, September, 2000]

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Palladium(II)-Catalyzed Michael-Type Addition Reactions Using Aryltin Compounds

Toshiyuki Ohe, Takeshi Wakita, Shin-ichi Motofusa, Chan Sik Cho, Kouichi Ohe, and Sakae Uemura*


Illustration

Aryltin compounds can be employed for Pd(II)-catalyzed Michael-type hydroarylation to , -unsaturated ketones and aldehydes in acetic acid. Slightly fewer than four aryl groups of tetraaryltins can be transferred to the products in the presence of a soluble metal chloride.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2157-2158 (2000) [Vol. 73, No. 9, September, 2000]

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Separation of Orientational Disorder in the X-Ray Analysis of the Kinetically Stabilized 2-Silanaphthalene

Keiji Wakita, Norihiro Tokitoh,*,, and Renji Okazaki,


Illustration

The structure of the kinetically stabilized 2-silanaphthalene was re-determined by X-ray crystallographic analysis at -180 °C. The crystal structure was refined more adequately than the previous results by the separation of the disorder of overlapped two 2-silanaphthalene moieties.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2159-2160 (2000) [Vol. 73, No. 9, September, 2000]

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Trialkylmanganate Mediated Radical Addition of Triphenylgermane to Carbon-Carbon Multiple Bonds

Hidenori Kinoshita, Hirotada Kakiya, and Koichiro Oshima*


Illustration

Treatment of 1-dodecyne with triphenylgermane in the presence of catalytic amount of tributylmanganate provided 1-triphenylgermyl-1-dodecene in good yield.

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Articles
Applied and Materials
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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2161-2167 (2000) [Vol. 73, No. 9, September, 2000]

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A Universal Structural Model for Human Hair to Understand the Physical Properties 1

Shinobu Nagase, Masato Ohshika, Shinya Ueda, Naoki Satoh, and Kaoru Tsujii*,


Illustration

Human hair consists of two structural parts, both of which have two (elastic and plastic) states, depending on the temperature (Two-part/two-state model). This structural model is powerful to generally explain the physical properties of human hair.

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Copyright (C) 2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 73, 2169-2177 (2000) [Vol. 73, No. 9, September, 2000]

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A Universal Structural Model for Human Hair to Understand the Physical Properties 2. Mechanical and Permeation Behaviors

Masahiko Sakai, Shinobu Nagase, Tomoyuki Okada, Naoki Satoh, and Kaoru Tsujii*,


Illustration

The two-part/two-state model for human hair proposed previously has been successfully applied to the mechanical and dye-permeation properties. Stress-strain curves over a wide range of temperature and the diffusion of dye molecules were analyzed using the model.

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