Chemistry Letters€¦ · dium(II) Complexes with Tridentate N-Heterocyclic Carbene Ligands Containing Aryloxy Groups and Their Application to Heck Reaction Cl1 N1 Pd1 O1 C1 Palladium

Chemistry Lettershttp://www.csj.jp/journals/chem-lett/

Vol.35 No.2 CMLTAGFebruary, 2006 ISSN 0366-7022

Copyright � 2006 The Chemical Society of Japan

Highlight Review

142 Heterolytic Dissociation of C–H Bond ofMethane over Agþ-exchanged Zeolites andConversion of Methane into Higher Hydro-carbons in the Presence of Ethene or Benzene

Ag+-exchanged Zeolite

ZO−Agn+ CH4

ZOδ-CH3δ+ + Agn-H

oror

CH3

ZO-H + Agn-H

H2

(ZO−: Zeolite lattice)

CC2H6 C2H4Toshihide Baba and Koji Inazu

Formation of highly polarized methoxy groups (ZO��CH3�þ) and silver hydride species (Agn–H) over Ag

þ-exchangedzeolites and reaction of the CH3

�þ with ethene and benzene form propene and toluene, respectively.

148 Chiral Symmetry Breaking in Chiral Crys-tallization and Soai Autocatalytic Reaction

N N

OH

R

N N

OH

R

N N

OH

R

N N

OH

R

SYMMETRY BREAKING

Ilya D. Gridnev

Complete chiral crystallization and absolute chiral synthesis are both fascinating phenomena shedding light on the pos-sible origins of homochirality in Nature and opening perspectives for efficient preparations of optically pure materials. Orig-inally, these two phenomena have been considered mechanistically quite different belonging to the hetero- and homogeneoussystems, respectively. However, the results of the active research in both fields undertaken in the last few years suggest thatthere may be a much closer likeness of the most important mechanistic features of these two phenomena. The present reviewbrings together the latest data on the complete chiral crystallization and absolute chiral synthesis including our own data onthe mechanism and spontaneous break of chirality in the Soai asymmetric autocatalysis.

C-20 Chemistry Letters Vol.35, No.2 (2006)

Copyright � 2006 The Chemical Society of Japan http://www.csj.jp/journals/chem-lett/

Letter

154 Syntheses and Characterization of Palla-dium(II) Complexes with Tridentate N-Heterocyclic Carbene Ligands ContainingAryloxy Groups and Their Application toHeck Reaction

Cl1

O1N1 Pd1

C1

Palladium carbene complex 1

I+ +

up to TON of 135,000

Heck reaction

Takeyoshi Yagyu, Shoko Oya, MasunobuMaeda, and Koichiro Jitsukawa

156 Anomalous 13CNMR Chemical Shifts ofHigh-spin Saddle Shaped Manganese(III)Octaethyltetraphenylporphyrin Complexes N

N

N

R R

R

R

R R

R

RMn

L

L'

(a) R = Et,(b) R = H,

L = CD3ODL = CD3OD

-600-400-2000200400

δ/ppm

meso(b)

meso(a)

Akira Ikezaki, Mikio Nakamura, and Ru-JenCheng

158 An Efficient Energy Transfer Found inTriphenylene/Hexaazatriphenylene Systemwith Electronic Complimentarity and Struc-tural Similarity

N

N

NN

NN

Ar

Ar

ArAr

ArAr

N O

Ar

Ar

ArAr

ArAr

Ar =

TP-excitation HAT-emissionEN-transfer

Tsutomu Ishi-i, Hiroshi Tashiro, RempeiKuwahara, Shuntaro Mataka, ToshitadaYoshihara, and Seiji Tobita

Electronic Supporting Information

160 Effect of Fluorine Substituent on theChitinase-catalyzed Polymerization of SugarOxazoline Derivatives

-2 -1 +1 +2 +3 +4

-2 -1 +1 +2 +3 +4

Fluorinated disaccharide oxazoline derivative

Fluorinated monosaccharide oxazoline derivative

HO OHO

N

F

CH3

O

1

O OHO

N

OH

CH3

O

HO OHO

NH

F

H3CO

2O

O OHO

NH

OH

H3CO

HO OHO

NH

F

H3CO

O OHO

NH

OH

H3CO

OHO

NH

F

H3CO

chitinase from Bacillus sp.

chitinase from Bacillus sp.

No oligomers

Fluorinated chitin polymerFluorinated chitin polymerAkira Makino, Junji Sakamoto, MasashiOhmae, and Shiro Kobayashi

162 Synthesis of Single-crystal BaMo2O7 Nano-wire Bundles: A General, Low-temperatureHydrothermal Approach to 1DMolybdenumOxide-based Nanostructures

Multicomponent BaMo2O7 single-crystalline nanowire bundles were synthesized by ahydrothermal crystallization process under mild conditions using cheap and simple bulky oxideand fluoride as precursors.

Peng Gao, Yi Xie, Lina Ye, Ying Chen, andZhen Li


Chemistry Letters Vol.35, No.2 (2006) C-21


164 Repetitive Two-step Method for OligoareneSynthesis through Rapid Cross-couplingof Hydroxyphenylboronic Acids and Anhy-drides

OTf

rapid cross-coupling

triflation

OH

R R

OTf

R n

(HO)2BOH

OBOH

OTf

R

Shunpei Ishikawa and Kei Manabe

166 Practical One-step Synthesis of SymmetricalLiquid Crystalline Dialkyloligothiophenesfor Molecular Electronic Applications

SS

S SS

SR R

1) n-BuLi,t-BuOK

n n2) RHal

80−93%Julie Leroy, Jeremy Levin, Sergey Sergeyev,and Yves Geerts


168 Synthesis and Characterization of Cyclopen-tadienone-annelated Hexadehydrodibenzo-[12]annulene

t-But-Bu

t-Bu t-Bu

O t-But-Bu

t-Bu t-Bu

O

+

Tsumoru Morimoto, Shuji Nagano, DaishiYokoyama, Masutaka Shinmen, KiyomiKakiuchi, Takashi Yoshimura, MotohiroSonoda, and Yoshito Tobe

170 Ordered CoSb3 Nanowire Arrays Synthe-sized by Electrodeposition

20 40 60 80 1000

1000

2000

3000

4000

18 21 24 270

840

420

Inte

nsi

ty/a

rb u

nit

2 /degreeθ

420

The XRD exhibits that only (420) and (840) peaks are discernible corresponding to a bccstructure with the lattice constant of a = 9.024 Å. In the experiment, we found that thesimultaneity of the nucleation, for CoSb3 nanowire, may not affect filling ratio of poresseriously and only influence the wire length.

Lijie Chen, Haining Hu, Yangxian Li, GuifengChen, Shuyun Yu, and Guangheng Wu

172 Design of Chiral Macrocyclic ComplexesBased on trans-Chelation of n:n Metal–Bidentate P,N- or N,N-Ligands N

N

O

Pri

NN

O

Pri

Pd

Cl

Cl

NN

O

Pri

NN

O

Pri

Pd

Cl

Cl

Pd PdClCl Cl

Cl>99%N

N

O

Pri

(1 equiv. each)

4 PdCl2(MeCN)2

+

Chiral self-assembled metallomacrocyclewith trans-chelation

4

28-membered ring

Manabu Hatano, Takafumi Asai, and KazuakiIshihara




174 Platelike Crystal Growth of Zn–Al LayeredDouble Hydroxide by Hot Water Treatmentof Sol–Gel Derived Al2O3–ZnO Films onGlass Substrate

XRD patterns of Al2O3−ZnO films (Al/Zn = 1)without the hot water treatment and with thehot water treatment for 15 min.

Inte

nsity

/ ar

b. u

nit

2θ / deg. ( Cu Kα)10 50403020

(a) without hot water treatment

[003

]

[006

]

(b) with hot water treatment

We have successfully immobilized Zn−Al

30 min, and then the films were immersed in

layered double hydroxide (LDH) filmsdirectly on glass substrates through thesol−gel method with hot water treatment.Porous Al2O3−ZnO thin films were originallyprepared on glass substrates by the sol−gelmethod with a heat treatment at 400 °C for

distilled water at 100 °C for 15 min to formnanocrystalline Zn−Al LDH with hexagonalstructure.

Naoko Yamaguchi, Tomohiko Nakamura,Kiyoharu Tadanaga, Atsunori Matsuda,Tsutomu Minami, and Masahiro Tatsumisago

176 Asymmetric Addition of Alkynylzinc Re-agents to Nitrones Utilizing Tartaric AcidEster as a Chiral Auxiliary

Weilin Wei, Masato Kobayashi, Yutaka Ukaji,and Katsuhiko Inomata

178 Solution Phase Synthesis of Hollow SnO2Nanospheres at Room Temperature

Hollow SnO2 nanospheres with diameters ranging from 100–120 nm have beensynthesized via template-directed approach at room temperature. A possible formationmechanism of the hollow SnO2 nanospheres is briefly discussed.

Qinghui Cao, Yongqian Gao, Xiangying Chen,Li Mu, Weichao Yu, and Yitai Qian


180 In situ Polymerization of Liquid CrystallineMonomers within Photoaligned MesoporousSilica Thin Film

Haruhiko Fukumoto, Shusaku Nagano, andTakahiro Seki

182 Hexa-, Hepta-, and Octacyclic Ladder Poly-silanes

R2Si

R2SiSiR SiR

RSi

RSi

SiR SiR

RSi

RSi

SiR

RSi

SiR

RSi

SiR SiR2

SiR2

RSiR2Si

R2SiSiR SiR

RSi

RSi

SiR SiR

RSi

RSi

SiR

RSi

SiR

RSi

SiR2

SiR2R2Si

R2SiSiR SiR

RSi

RSi

SiR SiR

RSi

RSi

SiR

RSi

SiR2

SiR2

5: R = i-Pr 6: R = i-Pr 7: R = i-Pr

Hexa-, hepta-, and octacyclic ladder polysilanes (5−7) were synthesized, and their structureswere determined by X-ray crystallography. These compounds have the double helix structureconsisting of two linear polysilane chains.

Soichiro Kyushin, Yoshinori Ueta, RyojiTanaka, and Hideyuki Matsumoto




184 Cation–�-driven Fluorescence Signalling ofAmmonium Cations by Naphthyl-substitutedZn10S16 and Cd10S16 Clusters

Zn10S16 and Cd10S16 clusters bearing twelve naphthalene units on the surface showedcharacteristic blue emission in response to the cation−π-mediated intercalative binding ofquaternary ammonium cations that allows the formation of ground-state naphthalene aggregates.

[Cd10S4(SNap)12Br4]4−

Q-ammonium ion

N++N

N+

N+N+

N+

N+

Weak Orange Emission Strong Blue EmissionKatsuaki Konishi and Takayuki Hiratani

186 Linear Relationship between Activity of aNew Ru-catalyst and Acidity of SubstitutedBenzoic Acids in the Dimerization of Acrylo-nitrile

y = −0.199x + 0.820R2 = 0.946

−0.1

−0.05

0

0.05

0.1

0.15

0.2

3.4 3.6 3.8 4.0 4.2 4.4 4.6

pKa

log(

VX

/VH

)

CNRCO2H

NCCN

NCCN

R O

OCN

NCCN

CN

2

3 4 5

Ru-based catalyst

11,4-dicyanobutene 1,4-dicyanobutane

1,4-dicyanobutadiene 2-cyanoethyl carboxylate propionitrile

A linear relationship between the activity of a ruthenium-catalyst and the acidity of m- and p-substituted benzoic acids in the dimerization of acrylonitrile was observed.

Relationship between log(VX/VH) and pKaof substituted benzoic acids

R: m- and p-X-C6H4

m-CN

m-Cl

m-MeO

p-Clm-Me

p-Me

p-MeO

o-PhCO

H

Kohichi Kashiwagi, Ryoji Sugise, ToshihiroShimakawa, Tunao Matuura, and MasashiShirai


188 Stereoselective Hydrogenation of Tetralin tocis-Decalin over a Carbon-supported Rhodi-um Catalyst in Supercritical Carbon DioxideSolvent

cis-Decalin was selectivelyobtained with high cis/transratio (83%) over a carbon-supported rhodium catalyst at 333 K under 6 MPa of hydrogen and 15 MPa of carbon dioxide.

H

H

H

H

83%

17%Norihito Hiyoshi, Eiichi Mine, ChandrashekharV. Rode, Osamu Sato, and Masayuki Shirai

190 An Efficient Synthesis of Helical MesoporousSilica Nanorods

Helical mesoporous silica nanorods have been synthesized with high efficiency by simply

using primary alcohol or amine as a cosurfactant during the synthesis of MCM-41.

Qinghong Zhang, Fei Lü, Changli Li, YeWang,and Huilin Wan

192 Fabrication of Ordered Nanostructuresin Ta Films Using 2D Array of FerritinMolecules as Template

Hideki Masuda, Yoshitaka Matsui, TetsuyaMiwa, Mitsutaka Nagae, Miyuki Tanji, andKazuyuki Nishio



194 (Inorganic Nanofiber/Enzyme) Hybrid Hy-drogel: Preparation, Characterization, andEnzymatic Activity of Imogolite/PepsinConjugate

Pepsin

HybridHydrogel

Imogolite: natural aluminosilicate nanofiber

Al-OH groupson surface

-PO3H2 group

Nozomi Inoue, Hideyuki Otsuka, Shin-IchiroWada, and Atsushi Takahara

196 Prediction of the Octanol/Water PartitionCoefficients of Petroporphyrin Model Com-pounds

The log POW values range from 5.8 (for 1a) to 10.1 (for 2c).

N N

NNVO

N N

NNVOR

R1

R2

1a−1b 2a−2c

R

R

R

R2

R2

R2R1

R1

R1

1a: R = CH3 1b: R = C6H52a: R1 = R2 = CH3 2b: R1 = CH3, R2 = C2H5 2c: R1 = R2 = C2H5Satsuki Asami and Koichi Saitoh

198 Palladium Catalyzed Conjugate 1,4-Additionof Organoboronic Acids to �,�-UnsaturatedKetones

Addition of chloroform is essencial for catalysis.

R2

O

R1

R2

O

R1

R2

O

R1

+

Ar Ar

ArB(OH)2

CHCl3, Base

Pd(0) / Phosphine

Tetsuya Yamamoto, Michiko Iizuka, TetsuoOhta, and Yoshihiko Ito

200 Kabob-like Carbon Nanotube Hybrids SEM image of the kabob-like carbon nanotube hybrids.

Yuyang Liu, Ronghua Wang, Wei Chen,Xianqiong Chen, Zhigang Hu, Xiaoyin Cheng,and Haozhong John Xin

202 Solid Synthesis of CsxH3�xPW12O40 Saltsand Their Catalytic Activity for the Isomeri-zation of n-Butane

5 0 -5 -10 -15 -20 -25

e

d

c

b

a

ppm

CsxH3−xPW12O40 salts were prepared by asolid-synthesis method and characterized withXRD, IR, N2 sorption, and

31P MAS NMR.They exhibit comparable catalytic activityfor n-butane isomerization to that preparedvia the liquid method.

Yan Zou, Bin Yue, Bin Zhang, and Heyong He



204 Development of Ordered Calcium CarbonateMicroarrays from Polymorph Specific Pla-nar Films

(a) (b)

(d)(c)

Ordered microarrays of rectangular

calcite, platy vaterite, and spicular

aragonite were selectively obtained

through overgrowth from planar films

prepared with polymeric species. We

successfully visualized the polymorphs

of the calcium carbonate films using the

overgrowth technique.Akiko Kotachi and Hiroaki Imai


206 Liposomal Sorting onto Substrate throughIon Recognition by Gemini Peptide Lipids

Stimulus A

Tagged liposomewith gemini peptide lipid

Stimulus BMasashi Otsuki, Yoshihiro Sasaki, ShintaroIwamoto, and Jun-ichi Kikuchi


208 Two-parameter Analysis of Solvent Effectson Selectivity in Chemical Reactions: Infor-mation of Polarity and Activation Volumeat the Transition State in Organic and Enzy-matic Reactions

The solvent effects on stereoselectivity (Σ) in theDiels−Alder reaction of cyclopentadiene (1), the[2 + 2]photodimerization of 2-cyclopentenone

(2), and the enzymatic asymmetrization of

prochiral 1,3-propanediols (3a−3c and 4) wereanalyzed by two-parameter treatment using both

the dielectric constant (ε) and the solubilityparameter (δ) to show a good linear relationship.

Σ = [major-isomer]/[minor-isomer]ln Σ = a[(ε − 1)/(2ε + 1)] + bδ2 + c

−1

2

3

4

1

0

ln Σ

(ob

s)

−1 10 2 3 4

Observed selectivity (ln Σ) vs calculatedselectivity (ln Σ), 1 ( ), 2 ( ), 3a ( ), 3b ( ),3c ( ), and 4 ( ).

ln Σ (calcd)

r = 0.985

Chunlei Lin, Yoshikazu Hiraga, and KatsuoOhkata

210 Protic, Imidazolium Ionic Liquids as Mediafor (Z)- to (E)-Alkene Isomerization

Ewa Janus, Marek Łożyński, and Juliusz Pernak

212 Rotaxane Synthesized by End-capping viaHydroruthenation of Axle Terminal Acety-lene and Its Derivation to �3-AllylrutheniumComplex-containing Rotaxane i) DB24C8ii) RuHCl(CO)(PPh3)3N

H2 O

PF6NH2

PF6O OO

O

OO

O

O

O

R

[Ru] Et2O

R

[Ru]

*[Ru] = RuCl(CO)(PPh3)2

R = Ph, Cy

"reactive" rotaxane

rotaxane formation

Hisahiro Sasabe, Nobuhiro Kihara, KazuhikoMizuno, Akiya Ogawa, and Toshikazu Takata



214 Fabrication of Gold Nanosheet and Nano-wire by Oxygen Plasma Induced Fusion ofDensely Arrayed Nanoparticles

One- and two-dimensionalfusion of densely packed goldnanoparticles was achieved byoxygen plasma treatment atroom temperature. Shin-ya Onoue, Junhui He, and Toyoki

Kunitake


216 Production of COx-free Hydrogen by AlkaliEnhanced Hydrothermal Catalytic Reform-ing of Biomass-derived Alcohols COx-free hydrogen could be

produced by hydrothermalcatalytic reforming processwhen Ca(OH)2 was added intothe reaction, and biomass-derived alcohols were used asthe reactants.

Yunpeng Xu, Zhijian Tian, Guodong Wen,Zhusheng Xu, Wei Qu, and Liwu Lin

218 Fabrication of a Novel Microfluidic DeviceIncorporating 2-D Array of Microbeads

Thomas Gumpenberger, Tadatake Sato, RyozoKurosaki, Aiko Narazaki, Yoshizo Kawaguchi,and Hiroyuki Niino

220 Syntheses, Structures, and Properties ofthe First Stable 1,10-Bis(diphosphenyl)-ferrocenes

Noriyoshi Nagahora, Takahiro Sasamori, andNorihiro Tokitoh


222 Bulk Synthesis of Poly(tert-butyl methacry-late) Long Macromonomer with NarrowDistribution by Atom Transfer Radical Poly-merization and Nucleophilic Substitution

1H NMR spectra of PtBMA macromonomer.

Wei Yang, Tatsuo Kaneko, Xiao-Ya Liu,Ming-Qing Chen, and Mitsuru Akashi




224 EXAFS Studies about the Sorption of Cad-mium Ions on Montmorillonite

Structural model for the Cd surface precipitate on montmorillonite.

3.39 Å3.39 Å

montmorillonite

surface precipitate

Rieko Takamatsu, Kiyotaka Asakura, Wang-Jae Chun, Tsuyoshi Miyazaki, and MasashiNakano

226 Ultrasound-promoted Highly Chemoselec-tive Reduction of Aromatic Nitro Com-pounds to the Corresponding N-Arylhydrox-ylamines Using Zinc and HCOONH4 inCH3CN

Zn/HCO2NH4,CH3CN,25-30°C

))))

NO2

R1

R2

NHOH

R1

R2Qi Xun Shi, Rong Wen Lu, Kun Jin, Zhu XiaZhang, and De Feng Zhao


228 Amorphous Carbon-promoted Low-temper-ature Crystallization of Silica

Akihiro Okabe, Makiko Niki, TakanoriFukushima, and Takuzo Aida


230 Photocatalytic Decomposition of Environ-mentally Persistent Perfluorooctanoic Acid

PFOA was photocatalytically decomposed by using TiO2/Ni−Cu, and a small bias potential (−0.1 V) applied on TiO2/Ni−Cu electrodegreatly enhanced its decomposition.

0

20

40

60

80

100

0 60 120 180 240 300 360Time/min

Dec

ompo

sitio

n /%

photolysisphotocatalysisphotoelectrocatalysis

Jing Chen, Pengyi Zhang, and Li Zhang

232 Importance of 30-Hydroxyl Group of theNucleosides for the Reactivity of ThymidinePhosphorylase from Escherichia coli

Thymidine phosphorylase replaced the base moiety of thymidine. We assume that this enzymerecognizes not only the base moiety but also the ribosyl hydroxyl group to fix the substrate.

Akihiko Hatano, Aiko Harano, and MasayukiKirihara



234 Oxygen Permeability of Surface-modifiedPoly(dimethylsiloxane) Characterized byScanning Electrochemical Microscopy

Scanning electrochemical microscopy (SECM) was employed to

quantitatively characterize the oxygen-permeation behaviors of

poly(dimethylsiloxane) (PDMS) and surface-modified PDMS by

positioning the microelectrode probe very close to sample surfaces.

The mass-transfer process of oxygen from the PDMS substrate to

the tip electrode is diffusion limited, whereas the oxygen permeability

of PDMS subjected to oxygen plasma treatment or albumin

adsorption is critically restricted. Our results suggest that PDMS-based

devices should be designed carefully since the oxygen permeability

of PDMS is possibly affected during a set of the device fabrication

procedure or cell culture within the PDMS microfluidic channels.

Hitoshi Shiku, Takeshi Saito, Ching-Chou Wu,Tomoyuki Yasukawa, Masaki Yokoo, HiroyukiAbe, Tomokazu Matsue, and Hiroshi Yamada

236 Separation of Americium(III) fromEuropium(III) by Dioctylammonium Dioc-tyldithiocarbamate/Nitrobenzene Extrac-tion

Am(III) is completely separated from Eu(III) in a neighborhood of pHeq = 6.

5 6 70

20

40

60

80

100

eq

Eu Am

%E

pH

Sunao Miyasita, Makoto Yanaga, Isamu Satoh,and Hideo Suganuma

238 Dehydrative Glycosylation in Water Using aBr�nsted Acid–Surfactant-Combined Cata-lyst

Naohiro Aoyama and Shū Kobayashi

Documents

Chemistry Letters€¦ · dium(II) Complexes with Tridentate N-Heterocyclic Carbene Ligands Containing Aryloxy Groups and Their Application to Heck Reaction Cl1 N1 Pd1 O1 C1 Palladium