Chemistry Letters http://www.csj.jp/journals/chem-lett/ Vol.36 No.7 CMLTAG July, 2007 ISSN 0366-7022 Copyright Ó 2007 The Chemical Society of Japan 820 Participation of Geminal Bonds in Organic Reactions R 2(1) R 1(2) R 2(1) R 1(2) R 1(2) R 2(1) C-R 1(2) : geminal bonds E,Z Reactivity E,Z Selectivity Yuji Naruse and Satoshi Inagaki The -bonds geminal to the -reacting center have been proposed to participate in the organic reactions via the cyclic transition states and to control the reactivity and the selectivity. An electron-donating geminal bond at the Z position enhances the reactivity of the olefins. An electron-donating bond prefers the Z position of the bond in the products of the reverse reactions. The effects of the geminal bond participation come from the orbital phase properties of the cyclic interactions including the geminal bonds. Highlight Review Letter 826 Lewis Acid Mediated Reactions of Allyl Chalcogenides with Ethyl Glyoxylate + EtO 2 C H O ChR EtO 2 C OH O ChR EtO 2 C SnCl 4 Ch = Te Ch = S, Se Kazunori Hirabayashi, Hideki Sato, Yu Kuriyama, Jun-ichi Matsuo, Soichi Sato, Toshio Shimizu, and Nobumasa Kamigata Electronic Supporting Information
820 Participation of Geminal Bonds in OrganicReactions
R2(1)R1(2)
R2(1)R1(2) R1(2)
R2(1)
C-R1(2): geminal bonds
E,Z Reactivity
E,Z SelectivityYuji Naruse and Satoshi Inagaki
The �-bonds geminal to the �-reacting center have been proposed to participate in the organic reactions via thecyclic transition states and to control the reactivity and the selectivity. An electron-donating geminal � bond at the Z positionenhances the reactivity of the olefins. An electron-donating � bond prefers the Z position of the � bond in the productsof the reverse reactions. The effects of the geminal bond participation come from the orbital phase properties of the cyclicinteractions including the geminal � bonds.
Highlight Review
Letter
826 Lewis Acid Mediated Reactions of AllylChalcogenides with Ethyl Glyoxylate
840 A Simple and Practical Method for thePreparation of Magnetite Nanowires
Single-crystalline magnetite nanowires were prepared by a facile hydrothermal process in thepresence of citrate anions and PVP at 180 °C for 24 h. The magnetite nanowires have diametersof 60−180 nm and length up to several ten micrometers. The nanowires were identified togrow along the [110] direction.
Yan Tang and Qianwang Chen
842 Fixation of CO2 by Hydroxozinc(II) Com-plex with Pyridylamino Type Ligand
844 Hydrogen Gas Sensing Properties of Calci-um Metaphosphate Glass-derived Hydrogels
0
20
40
60
80
0 500 1000 1500 2000
EM
F /
mV
Time / s
1
25
50
100
0
20
40
60
80
0 1 2 3 4 5
EM
F /
mV
ln(PH2I/PH2
II)
Potentiometric hydrogen gas sensors usingcalcium metaphosphate glass-derived hydrogelshowed good Nernstian response to hydrogengas concentration difference generated betweendetective and reference electrodes. The proton
to be almost 1; no contribution of Ca2+ and OH−transport number of the hydrogel was estimated
ions in the hydrogel was shown.
Takafumi Akamatsu, Hiroshi Osaki, YusukeDaiko, and Toshihiro Kasuga
Honeycomb-type SOFCs based on LSGM electrolyte was first time successfully built in onechannel used condition which is shown in schematic graph, and the maximum power densityof this cell can be achieved to a a high volumetric power as high as 300 W/L at 1073 K.
0.0 0.1 0.2 0.3 0.4 0.5 0.60.0
0.2
0.4
0.6
0.8
1.0
Current density/A cm–2
Pow
er d
ensi
ty/W
cm
–2
Vol
tage
/V
0.0
0.1
0.2
1073 KSchematic of 4-wall honeycomb cell Lead part
SSC cathode
NiFe91 anode
Pt mesh
Lead part
O2
H2
O2
O2 O2
Hao Zhong, Hiroshige Matsumoto, TatsumiIshihara, and Akira Toriyama
C-104 Chemistry Letters Vol.36, No.7 (2007)
Copyright � 2007 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/
848 Mild Oxidation of Styrene and Its Deriva-tives with Ionic Manganese PorphyrinImmobilized in the Similarly StructuredIonic Liquid
N N
NN
+
N+
N+
N+
Me
Me
Me
Me
Mn(III)N
PF6-
N+
BF4-
4 PF6-
(1c)
--
([BPy][BF4])
n -Bu
Ye Liu, Hong-Jiao Zhang, Yue-Qin Cai,Hai-Hong Wu, Xiu-Li Liu, and Yong Lu
Electronic Supporting Information
850 One-pot Preparation of Mesoporous SilicaParticles Having Mesopore Surface Func-tionalized with Poly(propylene oxide) Chains
Chihiro Urata, Yusuke Yamauchi, DaiMochizuki, and Kazuyuki Kuroda
Electronic Supporting Information
852 Synthesis of 1,10-Binaphthyl-2,20-diyl Phos-phoroselenoic Ammonium Salts and TheirConversion to Optically Active DialkylDiselenides
856 Surface Modification of Titania Particleswith Urushiol (Japanese Lacquer) and ItsApplication to the Preparation of Polymer–Titania Hybrids
Takeyuki Suzuki, Yusuke Ito, Bruno Boury,and Yoshiyuki Sugahara
Chemistry Letters Vol.36, No.7 (2007) C-105
Copyright � 2007 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/
858 A Novel Synthetic Route to Quinazoline-2,4-dione Dimer Derivatives
NH
CO2H
NH
N
O
ON N
O
HH2N-CO-NH-NH2 . HClN
N
O
ON N
O
OCH3
CH3
DMF+
1a-e 2a-d 2e
reflux
R1
R2
R3
R1
R2
R1
R2
or
Farzad Nikpour and Davood Sheikh
860 Selective Precipitation of Salts on the Surfaceof a Gel State Phosphatidylcholine Mem-brane
Precipitates of salts on dipalmitoyl phosphatidylcholine bilayers in Tris-buffered salinewere observed with an atomic force microscope and an X-ray fluorescence analyzer. Theprecipitates (γ) were found in a gel state DPPC (β), but not in a liquid-crystal state DPPC (α).The salts precipitated were considered to be NaCl in buffer.
γ β α
Kazutoshi Iijima, Teruhiko Matsubara, andToshinori Sato
862 Structural Characteristic of OutermostSurface of Cubic Mesoporous Silica Film
The outermost surface structure of a calcined cubic
showed a periodic pore arrangement with inherent cage
location of the grooves is shown by both red line and arrow.
mesoporous silica film was observed for the first time byhigh-resolution field emission scanning microscopy, which
openings and one dimensional grooves on the surface. TheTakashi Inoue, Itaru Gunjishima, Yoko Kumai,Shinji Inagaki, and Atsuto Okamoto
Electronic Supporting Information
864 Preparation and Reaction of Phenylsulfonyl-substituted Dizinciomethane
R O
R'
R
R'SO2Ph
PhSO2 Br
BrZn
PhSO2 ZnL
ZnL
β-TiCl3ZnI2
Treatment of dibromomethyl phenyl sulfone with zinc powder in the presence of a catalytic
converts a ketone or aldehyde into an alkenyl sulfone via a Wittig-type olefination reactionamount of lead in THF afforded phenylsulfonyl-substituted dinzinciomethane. The species
with the assistance of β-TiCl3.
Yoko Baba, Akio Toshimitsu, and SeijiroMatsubara
866 Structural Implication of OxoammoniumCations for Reversible Organic One-electronRedox Reaction to Nitroxide Radicals
Copyright � 2007 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/
868 Structural andMagnetic Properties of Co–NiNanowire Array Prepared by AlternatingCurrent Electrodeposition
Ordered Co43Ni57 nanowire array has been fabricated in a porous alumina template byalterrnating current electrodeposition. The as-obtained nanowire array has been characterizedby SEM, TEM, EDS, and XRD. Besides, The Co43Ni57 nanowire array has an obviousmagnetic anisotropy and a bad thermal stability at the medium temperature of 200 °C.
0 200 400 600
400
800
1200
1600
2000C.I.C.O.S.I.S.O.
Annealing temperature/ °C
Hc(
coer
civi
ty,O
e)
0.2
0.4
0.6
0.8
1.0
Squareness(M
r/Ms)
Jinxia Xu, Keyu Wang, and Yi Xu
870 Decomposition of Toluene by Liquid-phaseAtmospheric-pressure Microwave PlasmaGenerated Using Carbon Felt Pieces Impreg-nated with NaCl
(A) APSD, (B) LPAPMP, (C) APMP.
(A) (B) (C)
Hideki Kurihara and Tatuhiko Yajima
872 Rhenium-catalyzed Amidation of Heteroaro-matic Compounds via C–H Bond Activation
874 Immobilization of Palladium Acetate onIonic Liquid Copolymerized Polystyrene:A Way to Eliminate Inhibiting Effect of Imi-dazolium Chloride and Enhance CatalyticPerformance
N N Cl N N+
PS
Cl-
Styrene, AIBN
Ethanol, reflux, 24 hN N Cl-
Pd(OAc)2, r.t.
Ethanol, 24 hPd/PS-IL
Rie Sugimura, Kun Qiao, Daisuke Tomida,Yohei Kume, and Chiaki Yokoyama
Electronic Supporting Information
876 Characteristics of Amorphous TiO2 ParticlesPrepared in Various Reaction Systems
0
20
40
60
80
100
0 2 4 86 10 12
Irradiation time / h
Rel
ativ
e pe
ak a
rea
/ %
Relative peak area vs. irradiation time for commercial ( ), reverse micelle ( ), and reverseemulsion ( ). Catalyst heated at 200 °C; 150 mg, decomposed solution; 10 mL of a 0.03 mMMethyl Orange solution, light source; 30 mW/cm2 with cut-off filter 470 nm).(
Mariko Takayanagi, Yoko Imai, and KazuoTajima
Chemistry Letters Vol.36, No.7 (2007) C-107
Copyright � 2007 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/
878 Pd–Au Bimetal Supported on Rutile–TiO2
for Selective Synthesis of Hydrogen Peroxideby Oxidation of H2 with O2 under Atmo-spheric Pressure
Rutile TiO2 support is effective for increasing the formation rate as well as selectivity to2OH 2. A great enhancement in the H2O2 formation rate and selectivity is achieved by
controlling the particle size of Pd–Au.
Pd-Au(18nm)/Rutile TiO2
H2+O2
H2O2
99.7% selectivity
H2OTatsumi Ishihara, Yuiko Hata, Yohei Nomura,Kenji Kaneko, and Hiroshige Matsumoto
880 Self-assembly of Amphiphilic Benzo-15-crown-5 Azoprobes in Response to AlkaliMetal Ions in Water
Fuyuki Sato, Kouki Sakamoto, WakakoUmemoto, Takeshi Hashimoto, and TakashiHayashita
Electronic Supporting Information
882 Controlling Infiltration Pressure of a Nano-porous Silica Gel via Surface Treatment
Aijie Han and Yu Qiao
884 Magic-angle-spinning NMR at 30T with aHybrid Magnet
Solid-state 27Al MAS NMR at 30 T.400
300
200
100
0
FT P
ower
Int
ensi
ty /
arb
unit
150 100 50 0 -50
Shift / ppm
2.8 ppm27
Al-MAS-NMRMAS 15 kHz
30 T
Kenjiro Hashi, Tadashi Shimizu, TeruakiFujito, Atsushi Goto, Shinobu Ohki, KeijiShimoda, Yasuhiro Tobu, and Koji Saito
886 New Method for Synthesis of Aldehydesfrom Esters by Sodium Diisobutyl-t-butoxy-aluminum Hydride
Ali -Bu
OH
i -Bu Na
SDBBA
R OR'
O
0 °C R H
OAlH
DIBALH
i -Bu i -Bu
73−93%
NaO-t-Bu
Jung In Song and Duk Keun An
C-108 Chemistry Letters Vol.36, No.7 (2007)
Copyright � 2007 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/
888 Reversible Photon-mode PhosphorescenceSwitching of Heteroleptic CyclometalatedIridium(III) Complexes via PhotochromicBisthienylethene Switch Linked to AncillaryLigand
A novel class of phosphorescent photochromic IrIII complexes is reported. HeterolepticIr III complexes having a covalently tethered photochromic bisthienylethene (BTE) switchshowed optically addressable modulation of blue, green, and yellow phosphorescence.
Insuk Lee, Youngmin You, Seon-Jeong Lim,and Soo Young Park
Electronic Supporting Information
890 Hydrogen Production and MorphologicalChange of Chrysotile Asbestos in the Radiol-ysis of Aqueous Solutions
Noboru Aoyagi, Ryuji Nagaishi, FumitakaEsaka, and Reiji Yamada
892 A Dye-sensitized Solar Cell Using a RedRuthenium(II) Complex with 9,9-Bis(4-methoxyphenyl)-4,5-diazafluorene
RuNCS
NCS
N
N
MeO
MeO
N N
CO2HHO2C
RuNCSNCS
N
N
N N
CO2- TBA+
HO2C
CO2- TBA+
HO2C
= 7.3% = 7.0%
Solar energy-to-electricityconversion efficiency (η
904 Measurements of Ammonium and Sodiumsalt Aerosol Particles Using a Laser-ioniza-tion Single-particle Aerosol Mass Spectrome-ter
The chemical compositions of ammonium and sodium salt aerosol particles can be inferredfrom the distribution of ions in those negative-ion mass spectra obtained using a laser-ionizationsingle-particle aerosol mass spectrometer (LISPA-MS).
NO2-
NO3-
NH4NO3
200150100500m/z
O-
NO2-NO3
-
NaNO3-
NaNO4-
NaN2O4-
NaN2O5-
NaN2O6-
NaNO3
Rel
ativ
e ab
unda
nce
Masahiro Narukawa, Yutaka Matsumi, KenshiTakahashi, and Akihiro Yabushita
906 A Self-template Method for MesoporousOrganosilica Particles
This study describes the preparation of mesoporous organosilica particles using a simple self-template method and the effect of reaction variables such as the ratio of silane monomers onthe internal structure of organosilica particles.
PTMS + VTMS
PTMS VTMS
(a) Hydrolysis
Aqueous acidicsolution
Emulsion droplets
PTMS CondensedPTMS + VTMS
CondensedPTMS
Base
(b) Condensation
Compositeparticles
Mesoporous particles
Acetone
(C) Extraction
Sang Man Koo, Hoe Jin Hah, Dong Il Han, andChan Yoon Jung
Electronic Supporting Information
C-110 Chemistry Letters Vol.36, No.7 (2007)
Copyright � 2007 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/
908 Complexant-assisted Fabrication of FloweryAssembly of Hexagonal Close-packed CobaltNanoplatelets
Flowery assembly of single crystalline hexagonal
fabricated in high yield via a simple one-potclose-packed (hcp) cobalt nanoplatelets was
920 An Effect of Structural Modification in thePhoto-hydrogen-evolving RuIIPtII Dimers
0
0.01
0.02
0.03
0.04
0 1 2 3 4 5Irradiation time / h
N
N
COOH
CN
N
NN
NN
Ru
O
HN Cl
ClPt
2+
N
N
HOOC
CN
N
NN
NN
RuO
NH
Cl
ClPt
2+
H2
evol
ved
(mL/
10-m
L so
lutio
n)
The second example of a photo-hydrogen-evolving moleculardevice has been prepared andcharacterized to reveal that
sensitive to the structuralmodification at the spacer unitconnecting the RuII and PtII
the catalytic activity is quite
centers. Hironobu Ozawa and Ken Sakai
Electronic Supporting Information
922 Effect of Nanoparticle Addition into AnodeElectrodes for Direct Ethanol Fuel Cells
The mere addition of nanoparticles in PtRu/C anode increases DEFC perfromaces.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0 2 4 6 8 10
PtRu
SnO2 (21 nm)
TiO2 (20 nm)
SiO2 (7 nm)
SiO2 (14 nm)
I−V curves for DEFCcells consisting of nano-particles
PtRu: PtRu/C, SnO2: PtRu/C-n SnO2, TiO2: PtRu/C-n TiO2, SiO2: PtRu/C-n SiO2 Operation temperature: 25 °C, 1M ethanol in water for fuel.
Current density/mA·cm-2
Vol
tage
/V
Namsin Park, Takeyuki Shiraishi, KazuyoshiKamisugi, and Shuzi Hayase
924 EDTA-controlled One-pot Preparation ofNovel Shaped Gold Microcrystals and TheirApplication in Surface-enhanced RamanScattering
500 1000 1500 2000 2500
Raman Shift / cm-1
A
B
CD
390
1075 15
80
1139
1178
1387
1429
Inte
nsi
ty /
arb
un
it
Dawei Wang, Yang Liu, Xiaoguang Zhou,Jinying Sun, and Tianyan You
926 Color Surface Plasmon Resonance Imagingof Protein Microdot Arrays
True color image of IgG microdot arrays at different concentrations obtained at the incidentangle 44.34° by color surface plasmon resonance imaging method.
44.34°
0.05 mg/mL 0.50 mg/mL 1.00 mg/mL
aGangyi Shen, Zhiqiang Han, Wei Liu, and YiChen
C-112 Chemistry Letters Vol.36, No.7 (2007)
Copyright � 2007 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/
928 New Preparative Method of Aryl Tosylatesby Using Organobismuth Reagents
ArOTsMCPBA (1.1 equiv.)
− 78 to 0 °C, 10 min, then reflux, CH2Cl2
TsOH·H2O (2.8 equiv.)
Bi
Ar
SOO
72−91%
Naoto Sakurai and Teruaki Mukaiyama
Electronic Supporting Information
930 Diketobile Acids as New Hosts in Solid-stateEnantioselective Resolutions
New ketocholanic acid derivatives have been evaluated as hosts in the resolution ofaryl methyl sulfoxides and γ-lactames.
(R,S)-sulfoxide
COOH
O(R)-sulfoxide
(S)-sulfoxide
O
γ
Giancarlo Fantin, Marco Fogagnolo, DanielaPerrone, and Olga Bortolini
Electronic Supporting Information
932 A High Compensation Temperature of 175Kin a Vanadium Hexacyanochromate-basedMagnet
A high compensation temperature (Tcomp) of 175 K is observed in a vanadiumhexacyanochromate-based ferrimagnet, KI
0.19VII0.64(VIVO)0.36[CrIII(CN)6]0.73
• 7.5H2O, because
of the compensation of the positive sublattice magnetization of CrIII (S = 3/2) and the negativesublattice magnetizations of VII (S = 3/2) and VIV (S = 1/2).
S = 3/2
S = 3/2S = 1/2
KI0.19V
II0.64(V
IVO)0.36[CrIII(CN)6]0.73.7.5H2O
200
100
0
-100
Mag
netiz
atio
n / O
e cm
3 mol
-1
250200150100500Temperature / K
Tcomp = 175 K
@10Oe
@50Oe
VII VIVCrIIIN C C N
Shin-ichi Ohkoshi, Toshiya Hozumi, MikihisaMizuno, and Kazuhito Hashimoto
Electronic Supporting Information
934 Fabrication of a Novel Photoelectric Conver-sion Device Consisting of a Poly-3-dodecyl-thiophene Film and C60 Fullerene–Ethylene-diamine Nanoparticles
Nanoparticles consisting of C60 and ethylendiamine substantially enhanced the photocurrentsfrom the polythiophene film.
ITO
P3DT
C60P
hνMV
C60PC60Pe-
e-
e-
Ken-ichi Matsuoka, Hidetaka Seo, TsuyoshiAkiyama, and Sunao Yamada
936 Facile Synthesis of Self-aggregative ZincBacteriochlorins by Modifying NaturallyOccurring Chlorophyll-a
N
N N
N
OOCH3
Zn
O
OH
1
OH
OH7
8
31
Self-aggregative bacteriochlorin 1 was easily synthesizedfrom naturally occurring chlorophyll-a. Bacteriochlorin 1has OH moieties not only at the 31-position but also atthe 7,8-positions. The latter OH groups did not disturbself-aggregation of 1.Michio Kunieda, Kohei Yamamoto, Shin-ichi
Sasaki, and Hitoshi Tamiaki
Electronic Supporting Information
Chemistry Letters Vol.36, No.7 (2007) C-113
Copyright � 2007 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/
938 Synthesis andMesomorphism Study of NovelCarbohydrate-derived Liquid Crystals Con-taining Glucosyl and Chenodiolyl Residues
GCnDB
O
OR1
OO
OR1
OR1
OO
OR1
R1O
O
O
R1O
R1O
OO
R1O
OR1
O
O
OR1
n = 0, 4, 8R1: CC2H5O OO
OOC(CH2)n CO
Wenqiang Xiao, Baoyan Zhang, and YuehuaCong
Electronic Supporting Information
940 Preparation of Novel Polysaccharide Nano-particles by the Self-assembly of AmphiphilicPectins and Their Protein-encapsulationAbility
500 nm
self-assembly
amphiphilic pectin(pectin-graft-L-PAE)
nanoparticle
: L-PAE (L-phenylalanine ethyl ester)
Toshiyuki Kida, Keiichiro Inoue, TakamiAkagi, and Mitsuru Akashi
Electronic Supporting Information
942 Cation-exchange Resin as Efficient, Cost-ef-fective and Recyclable Catalyst for the Syn-thesis of 3-Propargylindoles
NH
Amberlyst-15
CH3CN, 80 °C+
OAc
R'R
NH
R R'
J. S. Yadav, B. V. Subba Reddy, G. G. K. S.Narayana Kumar, and K. V. Raghavendra Rao
944 Interface-initiated Emulsion Polymerization:Synthesis of Hollow Sphere with a Hole in theShell
PSt hollow spheres with a hole in the shell are prepared by the initial-initiated emulsionpolymerization. The sizes of the polymer sphere range from 0.5 to 2.3 µm.
Yun Chen, Zhen Qian, and Zhicheng Zhang
Electronic Supporting Information
946 Metathesis Reaction between Hydroxo(tetra-phenylporphinato)indium and Tetraphenyl-borate by Two-phase Reaction: Implicationto Liquid Membrane Anion Selective Elec-trode
Toshiyuki Baba, Yoshio Kanegawa, TakashiYasui, Kazutake Takada, and Akio Yuchi
Electronic Supporting Information
C-114 Chemistry Letters Vol.36, No.7 (2007)
Copyright � 2007 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/
948 Ultrasonic-mediated Preparation of Mesopo-rous Crystalline CdS Nanoparticle
Porous CdS nanoparticles with average pore size of 5.4 nm have been prepared by template-freeultrasonication route.
0.0 0.2 0.4 0.6 0.8 1.00
20
40
60
80
100
120
140
0 20 40 60 80 1000
2
4
6
8
Rel
ativ
e vo
lum
e (%
)
Pore range /A
Volu
me
/cm
3 .g-1
P/P oM. Sathish and R. P. Viswanath
950 Experimental Study on Gas-phase IonizationProcess for Ion Attachment Mass Spectrom-etry
Dimethylarsinic acid (DMAA)
This study could contribute to the
was detected by selective-ionmonitoring mode of ionattachment mass spectrometry(IAMS) and calculation of Li+
binding energy of N2 and DMAAwas performed. The resultsindicated the possibility of the
development and application of
transfer of Li+ from N2Li+ to
DMAA as the ion attachment
IAMS technique.
mechanism in IAMS analysis.
Lei Chen, Yaeko Suzuki, Kenji Hara, andTakashi Korenaga
952 Expression of Plasmid DNA Released fromDNA Conjugates of Gold Nanorods
Pulsed-laser irradiation induced release of plasmid DNA from DNA conjugates with goldnanorods (GNRs). Gel electrophoresis indicated that 1.2% of the plasmid DNA conjugatedwith GNRs was released from the conjugates. In vitro assays indicated that 0.47% of plasmidDNA was active.
Yukichi Horiguchi, Takuro Niidome, SunaoYamada, Naotoshi Nakashima, and YasuroNiidome
