and
Shohei Inoue*
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and
Shohei Inoue*
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Headline Articles
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Articles
General and Physical
=============================
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Kazuo Takemura,
and
Hideo Kawahara
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Takehara*
and
Hiroyuki Takemura
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and
Yoshiko Takemura
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Kazumasa Honda, and
Atsushi Masaki
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Articles
Analitical and Inorganic
=============================
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and
Michio Zenki
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ki
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and
Ken-ichi Okamoto
=============================
Articles
Orgainc and Biological
=============================
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C
Glycoside Rearrangement
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Yutaka Kameyama,
Marc Monnin,
Sigeru Torii,*
Michio Sasaoka,
Takashi Shiroi,
Shigemitsu Nagao,
Takae Yamada,
and
Yoshihisa Tokumaru
-Diazoacetates with Thioketene
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and
Toshikazu Ibata*
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ki,*
Yasushi Taguchi,
Tsutomu Miyasaka,
Mika Kitano,
Shinji Toyota,
Toshimasa Tanaka,
Katsumi Yonemoto,
and
Gaku Yamamoto
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=============================
Errata
=============================
,
'
-diyl Group as an
2
(
C
,
N
) :
3
(
C
,
C'
,
N
)-Bridging Ligand
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Copyright (C) 1995 The Chemical Society of Japan
=============================
Accounts
=============================
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1239-1246 (1995) [Vol. 68, No. 5, May, 1995]
and
Shohei Inoue*
A novel method, ``high-speed living polymerization", has been realized by using aluminium porphyrin as a nucleophilic initiator in conjunction with organoaluminium or organoboron compounds as Lewis acids. This is a fascinating method which enables us to synthesize uniform molecular-weight polymers within only a few seconds. The basic concept of this method involves the coordinative activation of monomer by a Lewis acid.
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=============================
Headline Articles
=============================
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1247-1262 (1995) [Vol. 68, No. 5, May, 1995]
New chiral bis(2-oxazolin-2-yl)pyridine-ruthenium complexes exhibited catalytic activity for the asymmetric cyclopropanation of olefins and diazoacetates in high trans : cis ratio up to 98 : 2 and in high enantioselectivity up to 98% ee.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1263-1268 (1995) [Vol. 68, No. 5, May, 1995]
The highly
,'
selective homocoupling reaction of allylic halides was achieved using barium reagent. The double-bond geometry of the starting allylic chloride was completely retained. The
,'
cross-coupling products were also prepared stereospecifically and regioselectively by this method.
=============================
Articles
General and Physical
=============================
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1269-1273 (1995) [Vol. 68, No. 5, May, 1995]
The linear variation of the vibrational relaxation rate (
v-1
) of the C=O stretching vibration of benzaldehyde with fm
, a parameter related to the microviscosity, density, and refractive index of the solvents exhibits a dependence of the relaxation time on the hydrodynamic and dispersion forces under the condition of high dilution.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1269-1273 (1995) [Vol. 68, No. 5, May, 1995]
The linear variation of the vibrational relaxation rate (v-1
) of the C=O stretching vibration of benzaldehyde with fm
, a parameter related to the microviscosity, density, and refractive index of the solvents exhibits a dependence of the relaxation time on the hydrodynamic and dispersion forces under the condition of high dilution.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1275-1279 (1995) [Vol. 68, No. 5, May, 1995]
Kazuo Takemura,
and
Hideo Kawahara
On the basis of the observation of absorption spectra of pH indicator dyes doped directly into LPD silica films, we have measured the effective acidity inside the LPD silica phases to be equivalent to pH=3.7 . The manifestation of strong acidity has been explained by the following silanol structure.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1281-1288 (1995) [Vol. 68, No. 5, May, 1995]
Imbricate structures of dimers are found for crystals of nematogenic CPn OB (n=6 , 7, and 8) and 6OPCB, while smectic-like layer structures are found for those of smectogenic 7OPCB and 8OPCB. The difference is related to the different magnitudes of longitudinal dipole moments due to the direction of the carbonyloxy group.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1289-1296 (1995) [Vol. 68, No. 5, May, 1995]
Takehara*
and
Hiroyuki Takemura
Self-assembled monolayers of 11-mercapto-1-undecanol, 11-mercapto-undecanoic acid, and 11-amino-1-undecanethiol were formed on a gold disk electrode and the effects of the terminal charges of the monolayers on the redox responses of 1,1' -ferrocenedimethanol, (ferrocenylmethyl)trimethylammonium, and ferrocenylsulfonate were evaluated by using voltammetric techniques.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1297-1304 (1995) [Vol. 68, No. 5, May, 1995]
and
Yoshiko Takemura
A polypyrrole (PPy)/poly(4-styrenesulfonate) composite film electrode, which was formed electrochemically in optimized conditions, showed good Nernstian responses only to monovalent cations. This potential response was influenced by both the electroactivity of the PPy and the content of the sulfonate group in the PPy matrix.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1305-1308 (1995) [Vol. 68, No. 5, May, 1995]
Kazumasa Honda, and
Atsushi Masaki
(-)-1-[4-(nitrophenylthio)ethyl]ferrocene, (+)-1-[4-(nitrophenylthio)ethyl]ruthenocene, and (+)-1-[4-(nitrophenylthio)ethyl]osmocene are shown to have the absolute configuration of R . These compounds were prepared by substitution of (R )-(-)-1-(hydroxyethyl)ferrocene, -ruthenocene, and -osmocene with 4-nitrobenzenethiol, showing that the substitution proceded with retention of configuration.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1309-1314 (1995) [Vol. 68, No. 5, May, 1995]
Ion-pair formation constants in water of 1 : 1 : 1 benzo-18-crown-6 (B18C6)-alkali metal (Na, K, Rb) picrate complexes were determined at 25 °C by solvent extraction. The overall extraction equilibrium constants were analyzed by four underlying equilibria. The fundamental equilibria which govern the highest extraction selectivity of B18C6 for K+ among the alkali metal ions are completely elucidated.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1315-1322 (1995) [Vol. 68, No. 5, May, 1995]
The CIDEP spectra of quasi-stable radical pairs formed in the laser photolysis of xanthone and several phenols in sodium dodecyl sulfate micellar solutions were studied. The steric bulkiness of phenol derivatives affects the kinetic parameters and interaction as the radical pairs in the micellar environment.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1323-1330 (1995) [Vol. 68, No. 5, May, 1995]
Amorphous n -C24 H50 prepared by vacuum deposition onto low-temperature substrates has disordered intra- and intermolecular conformations. By annealing, it is transformed into the ordered structure of the stable crystal. The relaxation process and the structure of the intermediate stages are discussed on the basis of the vibrational spectra.
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=============================
Articles
Analitical and Inorganic
=============================
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1331-1336 (1995) [Vol. 68, No. 5, May, 1995]
and
Michio Zenki
The structures of both 2-perimidinylammonium (PDA) bromide and PDA ethyl sulfate were determined by single-crystal X-ray diffractometry. The dimer of PDA was observed in both crystals. The fact that PDA is an excellent precipitant for the sulfate ion is attributed to the hydrogen-bonding of the dimer with the sulfate ion.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1337-1344 (1995) [Vol. 68, No. 5, May, 1995]
Formation of diastereomers of 
- and 
-[Co(en)3
]3+
was investigated in aqueous chiral-electrolyte solutions using 59
Co NMR spectroscopy. The differences in the 59
Co NMR parameters between the enantiomers of the complex cations were related to the extent of the ion-pair formation with chiral anions.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1345-1351 (1995) [Vol. 68, No. 5, May, 1995]
ki
Dynamic NMR study of the sulfur inversion in the dialkyl sulfide-gold complexes reveals that the inversion takes place via the pyramidal inversion mechanism both in the gold(I) and gold(III) complexes. The effect of oxidation state of the gold atom on the inversion barrier is discussed.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1353-1359 (1995) [Vol. 68, No. 5, May, 1995]
and
Ken-ichi Okamoto
A novel S-bridged CoIII
NiII
CoIII
trinuclear complex, [Ni{Co(aet)2
(en)}2
]4+
(
1
), is produced from the easy reaction of [CoCl2
(en)2
]+
and [Ni(aet)2
] in water.
1
selectively forms the racemic compound of
(C2
-cis
(S
))
(C2
-cis
(S
)) and
(C2
-cis
(S
))
(C2
-cis
(S
)) isomers. The H2
O2
oxidation of
1
causes the cleavage of the Ni-S bonds to give the mononuclear sulfinato complex, C2
-cis
(S
)-[Co(NH2
CH2
CH2
SO2
-N
,S
)2
(en)]+
(
2
).
1
and
2
are optically resolved and their structures are characterized by a combination of X-ray diffraction and absorption, CD, and NMR spectra.
=============================
Articles
Orgainc and Biological
=============================
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1361-1367 (1995) [Vol. 68, No. 5, May, 1995]
Aromatic hexahydrotriazines promptly reacted with butyl nitrite to yield N -nitroso-N -(n -butoxymethyl)arylamines in good yields when the contact between the two reagents was established at ca. 40 °C during 1 h.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1369-1377 (1995) [Vol. 68, No. 5, May, 1995]
The available syntheses of all of the diastereomers of 2,3-diaminobutanoic acids, found in some peptide antibiotics and toxins, were accomplished. The four isomers were all derived from mainly two pathways by one or two consecutive SN
2 reactions of the 
-substituent of
L
- and
D
-threonine derivatives.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1379-1384 (1995) [Vol. 68, No. 5, May, 1995]
C
Glycoside Rearrangement
C
-Glycosylation of acetylphloroglucinol 3,5-bis(alkyl ether) via O
C
glycoside rearrangement proceeds efficiently, to give the
-C
-glucoside, followed by aldol condensation to give the corresponding C
-glucosyl chalcone in an excellent yield.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1385-1391 (1995) [Vol. 68, No. 5, May, 1995]
Yutaka Kameyama,
Marc Monnin,
Sigeru Torii,*
Michio Sasaoka,
Takashi Shiroi,
Shigemitsu Nagao,
Takae Yamada,
and
Yoshihisa Tokumaru
Synthesis of 3-hydroxycephems from penicillin G was performed through the C=C bond cleavage of 1-(1-alkoxycarbonyl-2-chloromethyl-2-propenyl)-4-(phenylsulfonylthio)-2-azetidinones by successive treat-ment with RuCl3 /HIO4 and HIO4 /CuSO4 and subsequent reductive cyclization on treatment with a newly devised BiCl3 /Sn or TiCl4 /Sn bimetal redox couple in DMF containing pyridine.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1393-1400 (1995) [Vol. 68, No. 5, May, 1995]
-Diazoacetates with Thioketene
and
Toshikazu Ibata*
The Rh2
(OAc)4
-catalyzed reaction of allyl
-diazoacetates with di-t
-butylthioketene gave 4-allyl-2-methylene-1,3-oxathiolan-5-ones through the 1,5-cyclization of a thiocarbonyl ylide ylide followed by Claisen rearrangement with allene episulfide through the 1,3-cyclization of the intermediate. Other alkenyl and alkynyl diazoacetates also gave similar products.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1401-1407 (1995) [Vol. 68, No. 5, May, 1995]
Reactions of sulfoxides with magnesium amides generated from EtMgBr and secondary amines gave sulfides, dithioacetals, and/or vinyl sulfides depending upon the structure of the starting sulfoxides. The pathways leading to products involving the formation of the sulfur-stabilized carbonium ion intermediates are discussed.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1409-1436 (1995) [Vol. 68, No. 5, May, 1995]
A series of azulene analogues of triphenylmethyl cation (tri(1-azulenyl)methyl, di(1-azulenyl)phenylmethyl, and (1-azulenyl)diphenylmethyl hexafluorophosphates) were synthesized by hydride abstraction from the corresponding methane derivatives with DDQ. The dynamic stereochemistry of these cations was studied based on the temperature dependent 1 H NMR spectra, which were analyzed by a flip mechanism.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1437-1448 (1995) [Vol. 68, No. 5, May, 1995]
Sterically congested thiiranes having the 2,4,6-tri-t -butylphenyl (=Ar ) group were synthesized by reactions of (2,4,6-tri-t -butyl)thiobenzaldehyde with sterically hindered diazo compounds. The desulfurization, thermolysis, and photo-reaction of these sterically congested thiiranes were performed, and some unique products, for example, vinyl substituted Dewar benzene derivatives, were obtained.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1449-1454 (1995) [Vol. 68, No. 5, May, 1995]
-
D
-ManNAc-(14)-
-
D
-Glc-(12)-
L
-Rha, an anomerically modified trisaccharide component of the capsular polysaccharide of Streptococcus pneumoniae
type 19F, has been synthesized stereoselectively in 5.6% yield over 13 steps from
D
-glucose.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1455-1465 (1995) [Vol. 68, No. 5, May, 1995]
Optically active N
,N'
-bis(3-oxobutylidene)diaminatomanganese(III) complexes efficiently catalyzed aerobic enantioselective epoxidation of simple olefins. Several unfunctionalized olefins, such as cis
-
-substituted styrene derivatives, were led to the corresponding epoxides with good-to-high enantioselectivities. The key intermediate of the aerobic asymmetric epoxidation is also discussed.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1467-1472 (1995) [Vol. 68, No. 5, May, 1995]
The cyclo-condensation [piperidine, Ti(OR)4 , Al(OR)3 , and tetrabutylammonium fluoride catalysts] between silyl derivatives of 2-mercaptolkanoic acids and arylmethyleneamines proceeded with high stereoselectivity (cis /trans =50/1-1/25) to give alternatively both the cis -and trans -4-thiazolidinones, some of which are known as anti-platelet activating factor-active drugs.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1485-1496 (1995) [Vol. 68, No. 5, May, 1995]
ki,*
Yasushi Taguchi,
Tsutomu Miyasaka,
Mika Kitano,
Shinji Toyota,
Toshimasa Tanaka,
Katsumi Yonemoto,
and
Gaku Yamamoto
Diazotization of ap - and sc -2-(1,4-dimethyl-9-triptycyl)-2-methylpropylamines was carried out to find that the ap form gave an olefin, whereas the sc form did a cyclized compound as a major product. The new cyclic compound was identified by an independent synthesis.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1497-1507 (1995) [Vol. 68, No. 5, May, 1995]
Some indole and quinoline derivatives were produced from N -aryltrifluoroacetimidoyl radicals which were generated by three different methods: a tin-radical promoted reaction and the photochemical homolysis of the imidoyl iodides, and the thermal homolysis of imidoylazo-compounds.
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1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1509-1512 (1995) [Vol. 68, No. 5, May, 1995]
2,3-Dideoxy-2-fluoro- D -erythro -pentofuranose was prepared from 3-DPA lactone. The condensation reaction of 1-O -acetyl derivative of this sugar with silylated thymine in the presence of TMSOTf proceeded in poor stereoselective manner.
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=============================
Errata
=============================
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 1513-1513 (1995) [Vol. 68, No. 5, May, 1995]
,
'
-diyl Group as an
2
(
C
,
N
) :
3
(
C
,
C'
,
N
)-Bridging Ligand
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