Bimodal ¢ distribution was found. The results indicate that Soai's .... both reactive carbon atoms, the cycloreversion reaction was not suppressed. Additionally, no ...
BULLETIN OF THE
CHEMICAL SOCIETY OF JAPAN http://www.csj.jp/journals/bcsj/ Volume 82, Number 11, November 2009
■ Award Accounts The Chemical Society of Japan Award for Young Chemists for 2008
Molecular Theory Including Quantum Effects and Thermal Fluctuations Y. Shigeta
Recent progress in theoretical developments and applications, where the thermal fluctuations and quantum effects are important, are reviewed. Particularly, theoretical simulations of QM/MM molecular dynamics, of nuclear quantum effects, of electrons in a molecule driven by circularly polarized laser are shown.
Bull. Chem. Soc. Jpn. 2009, 82, 1323–1340
■ BCSJ Award Article Photoinduced Hydrogen-Evolution System with an AntibodyPorphyrin Complex as a Photosensitizer H. Yamaguchi, T. Onji, H. Ohara, N. Ikeda, and A. Harada
A complex between a monoclonal antibody for porphyrin and zincporphyrin was utilized to construct an energy conversion system. Hydrogen could be efficiently produced by the whole antibodyporphyrin complex. hν
ZnTCPP-Antibody Complex 20
COO
-
ZnTCPP-Antibody Complex
e
COO
15
H2 / µ M
N
and K. Nishikawa
ZnTCPP
5 Without Antibodies Pt
0 0
15
30
45
60
Time / min
65
Non-aromatic Aromatic
60 55 50 45 40 35
Bull. Chem. Soc. Jpn. 2009, 82, 1347–1366
Acceptor
COO
Antigen Binding Site
M1 / cm-1
Ultrafast Dynamics in Aprotic Molecular Liquids: A Femtosecond Raman-Induced Kerr Effect Spectroscopic Study H. Shirota, T. Fujisawa, H. Fukazawa,
L-Chain
N
- OOC
Bull. Chem. Soc. Jpn. 2009, 82, 1341–1346
10
N Zn N
H-Chain
4.0 4.5 5.0 5.5 6.0 6.5 (γ / d )1/2 / mL1/2 s-1
Ultrafast dynamics of forty aprotic molecular liquids has been studied by femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. A new correlation between the first moment of intermolecular vibrational spectra and the square root of the value of surface tension divided by liquid density has been found.
C64
Bulletin of The Chemical Society of Japan, Vol. 82, No. 11, November 2009
Reproducibilities of d³ bonds are investigated by calculating first-row transition-metal cationbenzene complexes. It is shown that electron correlations and long-range exchange effects are required to reproduce d³ bonds quantitatively in density functional theory calculations.
Theoretical Investigations on How to Reproduce d³ Bonds: Transition-Metal CationBenzene Complex Calculations T. Tsuneda, T. Hirosawa, Y. Nakatsuka, and K. Hirao
dx
Bull. Chem. Soc. Jpn. 2009, 82, 1367–1371
2
-y
Sc+
Data-Based Stochastic Approach to Absolute Asymmetric Synthesis by Autocatalysis B. Barabás, L. Caglioti, K. Micskei,
HOMO
SOMO
HOMO
SOMO
Bz ( E2u )
ScBz+ ( E2 )
Bz ( E2u )
ScBz2+ ( E2g )
2
Statistical distribution of enantiomeric excesses obtained by 121 parallel experiments of absolute asymmetric synthesis by asymmetric autocatalysis was analyzed. Bimodal ¢ distribution was found. The results indicate that Soai’s autocatalysis might operate by three concerted cooperating catalytic cycles.
and G. Pályi
A − Aldehyde R 2 Zn − i Pr 2 Zn Z, Z” − Chemical catalyst S, S” or R, R” − Stereochemical catalyst
R 2 Zn S A 2S Z” R2 Zn
Z S”
A 2S”
Bull. Chem. Soc. Jpn. 2009, 82, 1372–1376
An alternate linkage of [Co(hfac)2] and [Ni(pyterpy)2]2+ forms a 1D coordination polymer and twisting of them makes the polymer axially chiral. The polymers are assembled to form a host, which includes [Co(hfac)3]¹ complexes in a ¦/ª ratio of 3/1.
Formation of a Chiral Host with Axially Chiral Cationic 1D Coordination Polymers Composed of Achiral Building Blocks and Inclusion of Anionic Tris-Chelate Complexes in an Unbalanced ¦/ª Ratio J. Yoshida, S. Nishikiori, and R. Kuroda Bull. Chem. Soc. Jpn. 2009, 82, 1377–1385
The Single- and Double-Strand Cleavage of DNA by a Cationic Dicobalt Complex by Visible Light H. Shimakoshi, T. Kaieda, and Y. Hisaeda
A one-pot synthesis of a new polycationic organodicobalt complex with dual cationic alkyl groups as radical sources is reported. The dicobalt complex exhibited high ability for single- and double-strand DNA cleavage in comparison with that for the corresponding monocobalt complex by irradiation with visible light. N
+
N
+
Radical Assembled Effect
N
N O Co N CH2 O + N
O N Co O CH2
N
+
N N
CH2 +
Vis. light
Double-strand cleavage
+
+
Homolysis of Co-C bond
Bull. Chem. Soc. Jpn. 2009, 82, 1386–1392
N
Plasmid DNA Form I
Form II
Single-strand cleavage
http://www.csj.jp/journals/bcsj/
Form III
Bulletin of The Chemical Society of Japan, Vol. 82, No. 11, November 2009
Structural Relationships among Methyl-, Dimethyl-, and Trimethylammonium Phosphododecatungstates S. Busbongthong and T. Ozeki
C65
Structures of [(CH3)nNH4¹n]3[PW12O40]¢xH2O (n = 1, x = 2; n = 2 and 3, x = 0) were interpreted in terms of supergroupsubgroup relationships, revealing the influence of hydrogen bonds on lowering the symmetry of their crystals.
Bull. Chem. Soc. Jpn. 2009, 82, 1393–1397
Preparation and Structures of New Azobenzene Derivatives with a 3-Guaiazulenylvinyl Group S. Takekuma, K. Fukuda, T. Minematsu,
The title studies of new compounds 4 and 5 and structurally related new azobenzenes are reported.
and H. Takekuma
Bull. Chem. Soc. Jpn. 2009, 82, 1398–1408
Effect of Fluorous Tags on Glycosylation of Saccharide Primers in Animal Cells M. C. Z. Kasuya, M. Tojino, S. Nakano, M. Mizuno, and K. Hatanaka
5
4
Fluorous-tagged saccharide primers were synthesized and introduced to B16 cells. The lactoside primers were elongated by cellular enzymes and afforded GM3-type oligosaccharide while GlcNAc primers were galactosylated and afforded lactosamine derivatives that were further sialylated. OH HO HO
OH OH
O O (CH2)n(CF2)mF
HO
NHAc
OH
O
O HO
OH
O O (CH2)n(CF2)mF
OH
cells
Bull. Chem. Soc. Jpn. 2009, 82, 1409–1415
HO HOOC O HO OH O HO OH AcHN
OH
OH O OH
O HO
O
O (CH2)n(CF2)mF
NHAc
HO HOOC O HO OH O HO OH AcHN
OH
OH O OH
O HO
O
O (CH2)n(CF2)mF
OH
■ Selected Paper Differentially functionalized hexakis( psubstituted-phenylethynyl)benzene and hexakis[4-( p-substituted-styryl)phenylethynyl]benzene derivatives with various symmetries were synthesized and their optical properties were studied. Among them, hexakis[4-( p-dioctylaminostyryl)phenylethynyl]benzene showed the largest two-photon absorption cross-section of ¤ = 818 GM at 800 nm.
Synthesis and Optical Properties, Including Two-Photon Absorption Cross-Sections, of Differentially Functionalized Starburst-Type ³-Conjugated Molecules K. Kobayashi, Y. Kita, M. Shigeiwa, S. Imamura, and S. Maeda Bull. Chem. Soc. Jpn. 2009, 82, 1416–1425
http://www.csj.jp/journals/bcsj/
C66
Bulletin of The Chemical Society of Japan, Vol. 82, No. 11, November 2009
Two new chlorinated metabolites, fragilides F (1) and G (2), were isolated from the gorgonian J. fragilis. The structures of briaranes 1 and 2 were elucidated by spectral data analysis and the absolute configuration of 1 was determined by X-ray diffraction analysis. The relationships between proton chemical shifts and conformations of the methylenecyclohexane ring in briaranes possessing a C-11/20 carboncarbon double bond are described.
Discovery of New Chlorinated Briaranes from Junceella fragilis P.-J. Sung, S.-H. Wang, M. Y. Chiang, Y.-D. Su, Y.-C. Chang, W.-P. Hu, C.-Y. Tai, and C.-Y. Liu
AcO
OAc
OAc
AcO
AcO
O OH
Cl H OH AcO
Cl
Bull. Chem. Soc. Jpn. 2009, 82, 1426–1432
AcO O
O
AcO
Fragilide F (1)
O
O
O
Junceella fragilis
Cl
H
X-ray structure of fragilide F
Fragilide G (2)
Radical addition of bromotrichloromethane or perfluoroalkyl iodide to 2ethynyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane takes place in the presence of a radical initiator to afford the corresponding (E)-1-halo-1-alkenylboronic esters, which are useful intermediates that undergo cross-coupling reactions.
Radical Addition of Polyhaloalkanes to 2-Ethynyl-4,4,5,5-tetramethyl1,3,2-dioxaborolane T. Wada, Y. Sumida, A. Kondoh, H. Yorimitsu, and K. Oshima
radical initiator BrCCl 3 or R fI
O H C C B
(Rf)
O
Bull. Chem. Soc. Jpn. 2009, 82, 1433–1435
Preparation of MgAl Layered Double Hydroxide Intercalated with 2,7-Naphthalene Disulfonate and Its Selective Uptake of Aromatic Compounds from Aqueous Solutions T. Kameda, T. Yamazaki, and T. Yoshioka
Cl3C
O B O
H
Br (I)
MgAl layered double hydroxide intercalated with 2,7-naphthalene disulfonate ion was found to selectively take up specific aromatic compounds from aqueous solutions, attributed to the different extent of ³³ stacking interactions between the aromatic rings. X e-
Brucite-like layer −
SO3−
O3S
π - π stacking interaction
Y e-
Bull. Chem. Soc. Jpn. 2009, 82, 1436–1440
Unusual Photochromic Behavior of C3Methoxy-Substituted Bis(2-thienyl)perfluorocyclopentene K. Uchida, H. Sumino, Y. Shimobayashi, Y. Ushiogi, A. Takata, Y. Kojima, S. Yokojima, S. Kobatake, and S. Nakamura
Brucite-like layer 2,7-NDS•Mg-Al LDH
A novel photochromic diarylethene, bis(3-methoxy-2-thienyl)perfluorocyclopentene was synthesized. Although the derivative has methoxy groups at both reactive carbon atoms, the cycloreversion reaction was not suppressed. Additionally, no cyclization reaction was observed in the crystalline state even when the distance between the reactive carbon atoms was less than 0.4 nm.
F F S
Bull. Chem. Soc. Jpn. 2009, 82, 1441–1446
F F
F F F F MeO
UV
S
OMe
Type (I) http://www.csj.jp/journals/bcsj/
S Vis.
F F
F F MeO
OMe
S
