Easy formation of gold-like lustrous crystals with a high melting point from 1-aryl-2,5-bis[5-(tricyanoethenyl)-2-thienyl]pyrroles

Katsuyuki Ogura, Rui Zhao, Mingtao Jiang, Motohiro Akazome, Shoji Matsumoto, Kentaro Yamaguchi

Tetrahedron Letters 44(18) 3595-3598 2003年4月査読有り

A new class of π-conjugated organic compounds, 1-aryl-2,5-bis[5-(tricyanoethenyl)-2-thienyl]pyrroles that form gold-like lustrous crystals with a high melting point were obtained. The molecules in these crystals are arranged in a planar sheet to get close to each other via the intermolecular C-H⋯N hydrogen bond between the cyano nitrogen and the hydrogen of the nearest thiophene or pyrrole ring, which makes the crystals sparingly soluble in common organic solvents. © 2003 Elsevier Science Ltd. All rights reserved.
Structural Variation and Molecular Recognition using Inclusion Compounds of Crystalline Dipeptides

赤染元浩, 赤染元浩

有機合成化学協会誌 60 605-613 2003年1月査読有り
Novel organic crystals with red-violet metallic luster: 1-aryl-2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrrole derivatives bearing a heteroatom combined methyl substituent

Rui Zhao, Motohiro Akazome, Shoji Matsumoto, Katsuyuki Ogura

Tetrahedron 58(51) 10225-10231 2002年12月16日査読有り

A new class of π-conjugated organic compounds that form crystals with red-violet metallic luster were obtained upon introduction of a heteroatom combined methyl substituent (OMe, SMe, or NMe2) into the para-position of the central N-phenyl group of 1-phenyl-2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrrole. The molecule in crystals adopts a heaving ribbon-like molecular arrangement. This is obviously different from the planar arrangement of the gold-like analogues that bear halogen, cyano, or short alkyl group at para-position of the central N-phenyl group. Within the crystal lattice, an intermolecular C-H⋯N hydrogen bond occurs to make the adjacent π-systems (CN⋯C C) close enough, which is suggested to be responsible for the red-violet metallic color. © 2002 Published by Elsevier Science Ltd.
Supramolecular architecture of metal-lustrous inclusion crystals based on aromatic CH-π interaction: versatile inclusion of 1-(p-ethoxyphenyl)-2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrrole host with various electron-rich aromatic guest molecules

ZHAO R, MATSUMOTO S, AKAZOME M, OGURA K

Tetrahedron 58(51) 10233-10241 2002年12月16日査読有り
Sheet structure of an L,D-Dipeptide aggregate: Inclusion compounds of (S)-phenylglycyl-(R)-phenylglycine with amides

Motohiro Akazome, Kyoko Senda, Katsuyuki Ogura

Journal of Organic Chemistry 67(25) 8885-8889 2002年12月13日査読有り

A simple dipeptide, (S)-phenylglycyl-(R)-phenylglycine (S,R-1), formed inclusion compounds with a small amide such as formamide, acetamide, N,N-dimethylformamide (DMF), or N,N-dimethylacetamide. By single-crystal X-ray analysis, the inclusion compounds were shown to have a wavy layer structure. The molecules of S,R-1 are arranged in parallel via ionic pairing of the carboxyl and amino groups to construct the wavy layers. The guest molecules were accommodated in a channel cavity between the layers by means of hydrogen bonding with +NH3 of S,R-1. The cavity is surrounded by the phenyl groups of S,R-1 that conformationally rotate so as to make the cavity size fit the guest amide.
An important role of water in construction and destruction of the sheet structure in dipeptide aggregate

Motohiro Akazome, Toshiaki Takahashi, Ryo Ichi Sonobe, Katsuyuki Ogura

Tetrahedron 58(43) 8857-8861 2002年10月21日査読有り

Water molecules affect construction and destruction of inclusion crystals of a simple dipeptide (1). In the presence of water, the inclusion crystals, which have a water-buried dipeptide sheet structure, are smoothly constructed from amorphous solid of 1. But, the sheet is thermally unstable than anhydrous one. © 2002 Elsevier Science Ltd. All rights reserved.
Facile formation of stable crystals with gold-like metallic luster from organic molecules: 1-Aryl-2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrroles

Katsuyuki Ogura, Rui Zhao, Hiroyuki Yanai, Kazuhiro Maeda, Ryo Tozawa, Shoji Matsumoto, Motohiro Akazome

Bulletin of the Chemical Society of Japan 75(11) 2359-2370 2002年査読有り

The derivatives of 1-phenyl-2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrrole (1a) formed crystals with gold-like or bronze-like metallic luster. When a small substituent is located at the para position of the 1-phenyl group, gold-like lustrous crystals were formed. In contrast, the derivatives of 1 having a longer alkyl chain at the para position of the 1-phenyl group gave bronze-like crystals. The gold-like lustrous crystals have a sheet structure. In the sheet, the molecules of 1 are close to each other via the intermolecular interaction of cyano nitrogen with the hydrogen of the nearest thiophene or pyrrole ring, which enables the side-by-side interaction of the cyano group with the nearest thiophene and pyrrole rings. The bronze-like crystals have a lamella structure of the long alkyl chains that is sandwiched by two π-electron walls. In the wall, the 2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrrole moieties are arranged in a ribbon structure to interact to each other. The relationship of the arrangement of the 2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrrole moieties with the metallic color of the crystals is discussed.
A novel method for the construction of a benzene ring: A facile ring-closing reaction of (1E,3E,5E)-1-chloro-3-(p-tolylsulfonyl)-1,3,5-alkatrienes

Katsuyuki Ogura, Mineko Takeda, Jian R. Xie, Motohiro Akazome, Shoji Matsumoto

Tetrahedron Letters 42(10) 1923-1925 2001年3月4日査読有り

(1E,3E,5E)-1-Chloro-3-(p-tolylsulfonyl)-1,3,5-alkatrienes (1) underwent facile ring-closure followed by spontaneous removal of hydrogen chloride to form a benzene ring. This reaction sequence occurred at relatively low temperature. © 2001 Elsevier Science Ltd.
Inclusion of Poly(ethylene glycol)s by Crystalline (R)-(1-Naphthyl)glycyl-(R)-phenylglycine

Motohiro Akazome, Toshiaki Takahashi, Ryo Ichi Sonobe, Katsuyuki Ogura

Supramolecular Chemistry 13(1) 109-136 2001年査読有り

Crystallization of (R)-(1-naphthyl)glycyl-(R)-phenyl-glycine [(R,R)-1] in the presence of oligo(ethylene glycol) dimethyl ethers 2(n) or poly(ethylene glycol)s (PEGs, 3(Mn)) afforded inclusion compounds. The ratio of (R,R)-1/the guest polymer (2 or 3) was proportional to the length of the polymer chain. The crystal structure of a hepta(ethylene glycol) dimethyl ether-included compound was disclosed by X-ray crystallography which showed that (R,R)-1 molecules form a sheet and the guest molecule penetrates the crystal lattice of (R,R)-1 through a one-dimensional channel on the sheet Powder X-ray analysis revealed that, regardless of the length of the guest polymer, the distance between the neighboring sheets remains unchanged (12.0-123 Å) in these inclusion crystals. By thermal analysis, it was shown that the decomposition points of these inclusion compounds became higher with the longer PEG included. The inclusion phenomenon enabled the fractionation of PEGs with various molecular weights, among which longer PEG was preferably included.
Synthesis, solid-state structures, and aggregation motifs of phosphines and phosphine oxides bearing one 2-pyridone ring

M. Akazome, S. Suzuki, Y. Shimizu, K. Henmi, K. Ogura

Journal of Organic Chemistry 65(21) 6917-6921 2000年10月20日査読有り

Three phosphines and their corresponding oxides bearing one 2-pyridone ring and two benzene rings were synthesized. Their single-crystal X-ray analyses exhibited three kinds of molecular aggregation: bimolecular aggregates, chiral one-dimensional structures, and achiral one-dimensional structures. In the bimolecular aggregate of (2-oxo-1,2-dihydro-x-pyridyl)diphenylphosphines (x = 3: 2a and 6: 2c), cyclic dimers that are derived from two 2-pyridone rings are observed. In contrast, (2-oxo-1,2-dihydro-5-pyridyl)diphenylphosphine (2b) molecules form a chiral one-dimensional chain via intermolecular hydrogen bonding. In the case of phosphine oxides, their oxygen always acts as a hydrogen acceptor of the hydrogen bonding. Thus, (2-oxo-1,2-dihydro-x-pyridyl)diphenylphosphine oxides (x = 3: 3a and 5: 3b) form hydrogen bonds intermolecularly between the oxygen atom on the phosphoryl group and the hydrogen atom on nitrogen to construct a chiral or an achiral one-dimensional chain. Interestingly, (2-oxo-1,2-dihydro-6-pyridyl)diphenylphosphine oxide (3c) exists as a 2-hydroxypyridine form (enol form) in a crystalline state, and intermolecular hydrogen bonds between the phosphoryl oxygen and the hydroxy proton construct an achiral one-dimensional chain.
A chiral tweezers-type dicarboxylic acid: Studies on its complexation with amines utilizing CD spectrum

Hiroyuki Matsui, Sayuri Kushi, Shoji Matsumoto, Motohiro Akazome, Katsuyuki Ogura

Bulletin of the Chemical Society of Japan 73(4) 991-997 2000年4月査読有り

Complexation of a tweezers-type dicarboxylic acid (1) having an optically active π-system at its center with tertiary amines (triethylamine and DABCO) and secondary amines (piperidine and 4,4'-bipiperidine) was investigated under highly dilute conditions (about 6 x 10-5 mol dm-3) in CHCl3. The complex formation could be pursued with the CD spectrum of I which is markedly varied due to the titration of amines. The complexation process is discussed.
Salts of N,N'-oxalylbis(phenylglycine)s and 1-phenylethylamines: Structural variation of layered materials induced by stereochemistry

Motohiro Akazome, Toshiaki Takahashi, Naoyuki Ito, Noriyuki Baba, Katsuyuki Ogura

Tetrahedron 56(5) 753-761 2000年1月28日査読有り

Salts between (R,R)- or meso-N,N'-oxalylbis(phenylglycine) 1 and (R)-, (S)-, or (±)-1-phenylethylamine 2 construct three different layer structures depending on their stereochemistry. By X-ray crystallography, it is elucidated that the formation of a hydrogen bonding network between the amino and carboxyl groups and the planarity of the oxalyl functionality are important to construct the sheet structure. The salt of (R,R)-1 and 2 forms a bilayer or puckered structure, whereas the salt of meso-1 and 2 constructs a monolayer structure. (C) 2000 Elsevier Science Ltd.
Enantioselective inclusion of methyl phenyl sulfoxides and benzyl methyl sulfoxides by (R)-phenylglycyl-(R)-phenylglycine and the crystal structures of the inclusion cavities

Motohiro Akazome, Yuki Ueno, Haruko Ooiso, Katsuyuki Ogura

Journal of Organic Chemistry 65(1) 68-76 2000年1月14日査読有り

Crystalline (R)-phenylglycyl-(R)-phenylglycine [(R,R)-1] includes methyl phenyl sulfoxides (2 and 3) and benzyl methyl sulfoxides (4) with high enantioselectivity. The dipeptide exhibited different stereoselectivity depending on four structural isomers of methyl tolyl sulfoxide (C8H10OS): R for methyl 2-tolyl sulfoxide, S for methyl 3-tolyl sulfoxide, and racemic for methyl 4-tolyl sulfoxide. A structural isomer, benzyl methyl sulfoxide, was included in racemic form. Chlorophenyl methyl sulfoxides 3 (C7H7ClOS) with a similar volume showed the same enantioselectivity for their recognition. By single-crystal X-ray analyses of these inclusion compounds, it was elucidated that (R,R)-1 molecules self-assembled to form layer structures and included the sulfoxides between these layers and that the origin of the enantioselectivity based on chiral cavities was induced by conformation of the C-terminal phenyl group of the dipeptide. The relative position between the ammonio proton and the C-terminal phenyl group in one molecule of the dipeptide determined the stereochemistry of the methyl sulfinyl groups to be recognized. Various positional isomers of methyl xylyl sulfoxide having the formula of C9H12OS were subjected to the enantioselective inclusion by (R,R)-1 crystals and these results are also discussed.
Novel emitting materials for organic electroluminescent device: 1-aryl-2,5-di(2-thienyl)pyrrole derivatives having an electron-withdrawing group

Hiroyuki Yanai, Daisuke Yoshizawa, Satoshi Tanaka, Tatsuo Fukuda, Motohiro Akazome, Katsuyuki Ogura

Chemistry Letters (3) 238-239 2000年査読有り

Since 1-aryl-2,5-di(2-thienyl)pyrrole derivatives having an electron-withdrawing group emit strong fluorescence, they could be utilized as an efficient dopant in the emitting layer of an organic EL device. Especially, 1-aryl-2,5-di(2-thienyl)pyrrole having a ketene dithioacetal S,S-dioxide group showed extremely high performance (the highest luminous efficiency: 5.9 cd/A).
Novel appearance of chirality in a 2,5-di(p-tolyl)thiophene π-system by the aid of a remote chiral carboxyl group

OGURA K, MATSUI H, MATSUMOTO S, AKAZOME M, HARADA N

Tetrahedron Letters 40(51) 9065-9068 1999年12月17日査読有り
Enantiomeric Inclusion of α-Hydroxy Esters by (R)-(1-Naphthyl)glycyl-(R)-phenylglycine and the Crystal Structures of the Inclusion Cavities

AKAZOME M, TAKAHASHI T, OGURA K

The Journal of Organic Chemistry 64(7) 2293-2300 1999年4月査読有り
Efficient 1,2-asymmetric induction in radical reactions: Addition of acyl radicals to 3-hydroxy-1-(methylthio)-1-(p-tolylsulfonyl)-1-alkenes and their acetates

Katsuyuki Ogura, Takayuki Arai, Akio Kayano, Motohiro Akazome

Tetrahedron Letters 40(13) 2537-2540 1999年3月26日査読有り

Irradiation of aliphatic and aromatic aldehydes in the presence of benzophenone produces the corresponding acyl radicals which add to 3-hydroxy- 1-(methylthio)-1-(p-tolylsulfonyl)-1-alkenes and their acetates with high syn selectivity.
A Novel Synthesis of Highly Branched-Alkyl Aryl Ketones Using the Conjugate Addition of the Gilman Lithio Cuprate to β-Methylthio-α,β-unsaturated Ketones: Abnormal Reactivity of the Intermediary Enolates toward Molecular Oxygen

Chemistry Letters (2) 107-108 1999年査読有り
Novel photochemical addition of aromatic aldehydes to ketene dithioacetal S,S-dioxides and its application to organic synthesis

Katsuyuki Ogura, Takayuki Arai, Akio Kayano, Motohiro Akazome

Tetrahedron Letters 39(49) 9051-9054 1998年12月3日査読有り

On irradiation (>290 nm) in the absence or presence of benzophenone, various aromatic aldehydes add to ketene dithioacetal S,S-dioxides to give the corresponding 1:1 adducts, which were shown to be synthetic precursors of indanone derivatives.
Crystal Structure of Alkylammonium Salts of N,N’-Oxalylbis(phenylglycine)s: Optional Construction of a Monolayer or Bilayer Structure

AKAZOME M, TAKAHASHI T, OGURA K

Tetrahedron Letters 39(27) 4839-4842 1998年7月2日査読有り
Novel Reaction of Allylic Alcohols with a Hexafluoropropene-Diethylamine Adduct (PPDA) to Form α-Fluoro-α-(trifluoromethyl)-γ,δ-unsaturated Amides

OGU K, AKAZOME M, OGURA K

Tetrahedron Letters 39(3-4) 305-308 1998年1月15日査読有り
A Novel Nuceleophilic Addition to α-Fluoro-α-Trifluoromethyl-γ-LactonesA

Heterocycles 48(1) 15-20 1998年査読有り
High 1,2-Asymmetric Induction in Radical Reactions: Radical Addition to γ-Hydroxy α,β-Unsaturated Carboxylic Esters and Sulfones

Bulletin of the Chemical Society of Japan 70(12) 3091-3101 1997年12月査読有り
Specific Inclusion of 1,2-Dimethoxybenzene Derivatives by Crystalline (R)-Arylglycyl-(R)-phenylglycines and Its Structure

Motohiro Akazome, Yukiko Yanagita, Ryo Ichi Sonobe, Katsuyuki Ogura

Bulletin of the Chemical Society of Japan 70(11) 2823-2827 1997年11月査読有り

The crystallization of (R)-arylglycyl-(R)-phenylglycine (1, aryl=phenyl; 2, aryl=1-naphthyl) in the presence of 1,2-dimethoxybenzene or its derivatives affords an inclusion compound. A single-crystal X-ray analysis has shown that, in a 1,2-dimethyoxybenzene inclusion compound, dipeptide molecules arrange in a sheet and the 1,2-dimethoxybenzene lies at the end in a void between the sheets by being anchored to an ammonio hydrogen on the sheet via three-center hydrogen bonding. The distance between the sheets was found to be variable according to the length of the guest 1,2-dimethoxybenzene derivatives, as if they were pillars that support the sheets.
Highly stereoselective radical addition to 3-Hydroxy-1-(methylthio)-1-(p-tolylsulfonyl)-1-alkanes and its application to the preparation of optically active compounds

Akio Kayano, Motohiro Akazome, Makoto Fujita, Katsuyuki Ogura

Tetrahedron 53(36) 12101-12114 1997年9月8日査読有り

Efficient 1,2-asymmetric induction was realized in the addition of a 1-hydroxyalkyl radical (R2Ċ-OH to 3-hydroxy-1-methylthio)-1-(p-tolylsulfonyl)-1-alkenes and their acetates (1): Irradiation of 1 and benzophenone in an alcohol (R2CHOH) gave an adduct (2) with a high syn selectivity. Optically active 1 is easily obtainable by means of lipase PS-catalyzed transesterification and, therefore, the present radical asymmetric induction provides a synthetic route lending to various chiral compounds.
Asymmetric recognition of 1-arylethylamines by (R)-phenylglycyl-(R)-phenylglycine and its mechanism

Motohiro Akazome, Hirozumi Matsuno, Katsuyuki Ogura

Tetrahedron Asymmetry 8(14) 2331-2336 1997年7月24日査読有り

An unprotected dipeptide, (R)-phenylglycyl-(R)-phenylglycine, which is insoluble in water, was shown to be an excellent resolving reagent for racemic 1-arylethylamines. By simply stirring the mixture of the dipeptide and racemic 1-phenylethylamine in presence of water, asymmetric recognition occurred to give a salt of (S)-1-phenylethylamine (95% ee) and the dipeptide. X-Ray crystallographic study of the salt elucidated the crystal structure of the diastereomeric salt, where hydrogen bonding and hydrophobic interaction between the dipeptide and amines play important roles in the construction of layers.
Stereoselective Formation of α-Fluoro-α-trifluoromethyl-γ-lactones Starting from γ-Hydroxy-α,β-unsaturated Sulfones and a Hexafluoropropene-Diethylamine Adduct (PPDA)

OGURA K, OGU K, AYABE T, SONEHARA J, AKAZOME M

Tetrahedron Letters 38(29) 5173-5176 1997年7月21日査読有り
Enantiomeric recognition of alkyl phenyl sulfoxides by crystalline (R)-phenylglycyl-(R)-phenylglycine

Motohiro Akazome, Makoto Noguchi, Osamu Tanaka, Atsuko Sumikawa, Tohru Uchida, Katsuyuki Ogura

Tetrahedron 53(25) 8315-8322 1997年6月23日査読有り

The inclusion compounds of several alkyl phenyl sulfoxides by (R)-phenylglycyl-phenylglycine [(R,R)-1] were prepared by two different methods (sorption and crystallization). Alkyl phenyl sulfoxides entered crystalline (R,R)-1 with high S-enantioselectivity except for methyl phenyl sulfoxide which was recognized with high and reverse enantioselectivity (R-from in 92% ee). From the X-ray crystallographic study of an inclusion compound of bis[(o-methylsulfinyl)benzyl]ether (3) and (R,R)-1, it is deduced that the reversal of enantioselectivity was achieved by the conformational change of phenyl groups on the dipeptide layer.
Optional Formation of “Parallel or Antiparallel” β-Sheet-like Structures in (R)-(1-Naphthyl)glycyl-(R)-phenylglycine Crystals

Chemistry Letters (11) 995-996 1996年査読有り
Ruthenium Complex-Catalyzed Reductive N-Heterocyclization : Novel Synthesis of 1-Pyrroline Derivatives from γ-Nitrocarbonyl Compounds

WATANABE Y, YAMAMOTO J, AKAZOME M, KONDO T, MITSUDO T

The Journal of Organic Chemistry 60(26) 8328-8329 1995年12月1日査読有り
Novel Synthesis of γ-Lactones Starting from β,γ-Unsaturated Carboxylic Esters

Bulletin of the Chemical Society of Japan 68(12) 3599-3609 1995年12月査読有り
Palladium complex-catalyzed intermolecular reductive N-heterocyclization: novel synthesis of quinazoline derivatives from 2-nitrobenzaldehyde or 2-nitrophenyl ketones with formamide

Motohiro Akazome, Jun Yamamoto, Teruyuki Kondo, Yoshihisa Watanabe

Journal of Organometallic Chemistry 494(1-2) 229-233 1995年5月31日査読有り

A combination of the palladium complex PdCl2(PPh3)2 with MoCl5 shows a high catalytic activity for the intermolecular reductive N-heterocyclization of 2-nitrobenzaldehyde or 2-nitrophenyl ketones with formamide to give the corresponding quinazoline derivatives in moderate yields. For example, in the reaction of 2-nitrobenzaldehyde with formamide, quinazoline was obtained in 46% yield. We assume that the present reaction proceeds via an active nitrene intermediate which would be generated by selective deoxygenation of nitro group by carbon monoxide. © 1995.
Efficient 1,2-Asymmetric Induciion in Radical Reactions: Stereoselective Radical Addition to 3-Hydroxy-l-(methylthio)-l-(p-tolylsulfonyl)-l-alkenes

Katsuyuki Ogura, Akio Kayano, Naoko Sumitani, Motohiro Akazome, Makoto Fujita

Journal of Organic Chemistry 60(5) 1106-1107 1995年3月1日査読有り
Palladium Complex-Catalyzed Reductive N-Heterocyclization of Nitroarenes: Novel Synthesis of Indole and 2H-Indazole Derivatives

Motohiro Akazome, Teruyuki Kondo, Yoshihisa Watanabe

Journal of Organic Chemistry 59(12) 3375-3380 1994年6月1日査読有り

The dichlorobis(triphenylphosphine)palladium (PdCl2(PPh3)2)-tin(II) chloride (SnCl2) system shows high catalytic activity for the reductive N-heterocyclization of various 2-nitrostyrene and N-(2- nitrobenzylidene)amine derivatives when employed at 100 °C for 16 h under 20 kg cm−2 of initial carbon monoxide pressure, to give the corresponding indole and 2H-indazole derivatives in good yield. For example, 2-phenylindole was obtained in 75% yield from the reductive N-heterocyclization of 2-nitrostilbene. Similarly, 2-propyl-2H-indazole was readily prepared in 83% yield by the reductive N-heterocyclization of N-(2-nitrobenzylidene)propylamine. A nitrene intermediate for the present reaction is proposed on the basis of deuterium-labeling experiments and the investigation of alkyl rearrangement in the construction of the indole skeleton. Carbon monoxide effectively operates as a deoxygenating agent of the nitro group to afford a nitrene intermediate. © 1994, American Chemical Society. All rights reserved.
Novel Reactions Catalyzed by Transition Metal Carbonyls

Yoshihisa Watanabf, Take Aki Mitsudo, Teruyuki Kondo, Kenji Wada, Motohiro Akazome

Sekiyu Gakkaishi (Journal of the Japan Petroleum Institute) 37(5) 471-479 1994年査読有り

Iron, cobalt, and ruthenium carbonyls show novel catalytic activities. The Fe(CO)5/S system is an excellent catalyst precursor for coal liquefaction using carbon monoxide water, syngas/water, and carbon monoxide/alcohol as hydrogen sources. The carbonyl trinuclear ferrate/KOH/support system exhibits high catalytic activity with high selectivity for lower olefins in Fischer-Tropsch synthesis. Using Co2(CO)8/N-silylamine, a variety of cyclic ethers are smoothly carbonylated to give the corresponding siloxy amides. The Ru-catalyzed C-H bond activation of a variety of formyl groups is widely applicable for hydroamidation, hydroesterification, and hydroacylation of olefins using formamides, formates, and aldehydes, respectively. The Ru3(CO)12/carbon monoxide system is effective for deoxygenative transformation of oximes and nitroarenes. Ketoximes, amidoximes, and aldoximes are converted into ketimines, amidines, and aldimines, respectively. N-(2-Nitrobenzoyl)amide is converted into a quinazolinone derivative via a nitrene intermediate. © 1994, The Japan Petroleum Institute. All rights reserved.
Ruthenium complex-catalyzed selective deoxygenation of amidoximes to amidines and its application to the facile synthesis of pyrimidines

Motohiro Akazome, Teruyuki Kondo, Yoshihisa Watanabe

Journal of Molecular Catalysis 80(3) 383-393 1993年4月査読有り

Ru3 (CO)12 showed a high catalytic activity for the selective deoxygenation of aromatic and N-heteroaromatic amidoximes to the corresponding amidines at 80°C for 5 h under carbon monoxide pressure (5 kg cm-2 ). For example, the deoxygenation of benzamidoxime afforded benzamidine in 82% yield. Furthermore, the present deoxygenation reaction of amidoximes catalyzed by Ru3 (CO)12 was applied to the one-pot synthesis of pyrimidine derivatives. When the deoxygenation of amidoximes was carried out in the presence of 1,3-dicarbonyl compounds such as acetylacetone, acetylacetophenone, and ethyl acetoacetate, the corresponding pyrimidine derivatives, which were the condensation products of the generated amidines with 1,3-dicarbonyl compounds, were obtained in up to 93% yield. © 1993.
Transition-Metal Complex-Catalyzed Reductive N-Heterocyclization: Synthesis of 4(3H)-Quinazolinone Derivatives from N-(2-Nitrobenzoyl)amides

Motohiro Akazome, Teruyuki Kondo, Yoshihisa Watanabe

Journal of Organic Chemistry 58(2) 310-312 1993年査読有り

Several ruthenium and platinum complexes smoothly catalyze the reductive N-heterocyclization of N-(2-nitrobenzoyl)amides under carbon monoxide pressure to afford the corresponding 4(3H)-quinazolinone derivatives, including some quinazolinone alkaloids, in good yields. © 1993, American Chemical Society. All rights reserved.
Lanthanide(II) iodide catalysed photochemical allylation of aldehydes with allylic halides

Teruyuki Kondo, Motohiro Akazome, Yoshihisa Watanabe

Journal of the Chemical Society, Chemical Communications (11) 757-758 1991年査読有り

Lanthanide(II) iodides such as Sml2 and Ybl2 show high catalytic activity for the photochemical allylation of aldehydes with allylic halides to give the corresponding homoallylic alcohols.
Palladium complex-catalysed reductive N-heterocyclization of N-(2-nitrobenzylidene)amines into 2H-indazole derivatives

Motohiro Akazome, Teruyuki Kondo, Yoshihisa Watanabe

Journal of the Chemical Society, Chemical Communications (20) 1466-1467 1991年査読有り

Dichlorobis(triphenylphosphine)palladium-tin(II) chloride system effectively catalyses the selective transformation of N-(2-nitrobenzylidene) amines into the corresponding 2H-indazole derivatives under carbon monoxide via a reductive N-heterocyclization reaction.
RUTHENIUM COMPLEX CATALYZED SELECTIVE DEOXYGENATION OF KETOXIMES TO KETIMINES

M AKAZOME, Y TSUJI, Y WATANABE

CHEMISTRY LETTERS (4) 635-638 1990年4月
Ruthenium Complex Catalyzed Intermolecular Hydroacylation and Transhydroformylation of Olefins with Aldehydes

Teruyuki Kondo, Motohiro Akazome, Yoshihisa Watanabe, Yasushi Tsuji

Journal of Organic Chemistry 55(4) 1286-1291 1990年査読有り

Low-valent ruthenium complexes such as dodecacarbonyltriruthenium (Ru3(CO)12), (η4-l,5-cyclooctadiene)(η6-l,3,5-cyclooctatriene)ruthenium (Ru(COD)(COT)) and bis( η6- cyclooctadienyl)ruthenium showed high catalytic activity for the intermolecular hydroacylation of olefins with various aromatic and heteroaromatic aldehydes at 180–200 °C for 24–48 h under an initial carbon monoxide pressure of 20 kg cm-2to give unsymmetric ketones in moderate to good yields. In the reaction of 2-thiophenecarbaldehyde with cyclohexene, cyclohexyl 2-thienyl ketone was obtained in 62% yield. On the other hand, when the aliphatic aldehyde, heptanal, was treated with cyclohexene, the corresponding ketone was not obtained at all, and a transhydroformylation reaction proceeded; i.e., the formyl group of heptanal was apparently transferred to cyclohexene to give cyclohexanecarbaldehyde in 29% yield, together with their Tishchenko-type reaction products. © 1990, American Chemical Society. All rights reserved.
A new π-system: 1-aryl-2,5-di(2-thienyl)pyrroles
Efficient Addition of Aroyl Radicals to Ketene Dithioacetal S,S-Dioxides and its Utilization in Origanic Synthesis

MISC

ヨウ化水素による共役エノンおよびα，β－不飽和カルボン酸誘導体の選択的オレフィン還元反応

丸本颯人, 赤染元浩, 大谷康彦, 海宝龍夫, 松本祥治

SIS Report（ヨウ素学会会報) (23) 2020年11月
環状チオアミジウム塩および環状イミダゾイソキノリニウム塩の求核試薬に対する反応性

綿貫祥汰, 高田大貴, 赤染元浩, 松本祥治

ヨウ素 (22) 2019年
Corrigendum to “Selective reaction of benzyl alcohols with HI gas: Iodination, reduction, and indane ring formations” (Tetrahedron (2017) 73(52) (7254–7259), (S0040402017311456) (10.1016/j.tet.2017.11.009))

Shoji Matsumoto, Masafumi Naito, Takehisa Oseki, Motohiro Akazome, Yasuhiko Otani

Tetrahedron 74(48) 6959-6960 2018年11月29日査読有り

© 2018 Elsevier Ltd The authors regret that, in the published article, they have represented the product from 2-(naphthalene-2-yl)propan-2-ol (1g) as 1,3,3-trimethyl-1-(naphthalen-2-yl)-2,3-dihydro-1H-cyclopenta[a]naphthalene (wrong 4m). But the product could be assigned as 1,1,3-trimethyl-3-(naphthalen-2-yl)-2,3-dihydro-1H-cyclopenta[b]naphthalene (right 4m) using 500 MHz NMR on a JEOL JNM-ECA500 spectrometer because the three singlet peaks were found at 7.83 ppm and at 7.85 ppm (as two singlet peaks) in the spectrum. Thus, they wish to correct the structure of wrong 4m into right 4m in the manuscript. The reason for the selective formation of right 4m would be caused by the less steric hinderance at 3 position of naphthalene. The reference of proton data also agreed with the structure (right 4m).1 The data of the melting point (116–117 °C) was near to the data for wrong 4m (122–124 °C2) compared with the data for right 4m (colorless viscous liquid)1. [Figure presented] Corrected data 1,1,3-trimethyl-3-(naphthalen-2-yl)-2,3-dihydro-1H-cyclopenta[b]naphthalene (4m) Colorless solid: mp 116–117 °C; 1H NMR (CDCl3, 500 MHz) δ 1.40 (s, 3H), 1.45 (s, 3H), 2.08 (s, 3H), 2.36 (d, J = 13.5 Hz, 1H), 2.47 (d, J = 13.5 Hz, 1H), 7.10 (dt, J = 1.2 and 7.2 Hz, 1H), 7.21 (dd, J = 1.9 and 8.7 Hz, 1H), 7.29 (dt, J = 0.9 and 7.0 Hz, 1H), 7.37 (d, J = 8.5 Hz, 1H), 7.41 (d, J = 8.4 Hz, 1H), 7.42 (dt, J = 1.6 Hz and 8.2 Hz, 1H), 7.46 (dt, J = 1.4 and 6.9 Hz, 1H), 7.65 (d, J = 8.6 Hz, 1H), 7.76 (d, J = 7.9 Hz, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.83 (s, 1H), 7.85 (s, 2H). Original data Colorless solid: mp 116–117 °C; 1H NMR (CDCl3, 300 MHz) δ 1.40 (s, 3H), 1.45 (s, 3H), 2.08 (s, 3H), 2.36 (d, J = 13.5 Hz, 1H), 2.47 (d, J = 13.5 Hz, 1H), 7.09 (t, J = 7.0 Hz, 1H), 7.21 (dd, J = 1.9 and 8.6 Hz, 1H), 7.29 (t, J = 7.0 Hz, 1H), 7.35–7.48 (m, 4H), 7.65 (d, J = 8.7 Hz, 1H), 7.75–7.85 (m, 5H). [Figure presented] The authors would like to apologise for any inconvenience caused.
Development of novel primer material suitable for COP film and Ag nano-ink

Taiki Yamate, Eiko Mieda, Kazuhisa Kumazawa, Hiroshi Suzuki, Motohiro Akazome

Proceedings of the International Display Workshops 1 313-316 2015年査読有り

© 2015 Society for Information Display. We have developed a unique organic-inorganic hybrid coating agent suitable for a primer which connects Ag nano-ink to COP film. This material forms the glass-like surface on the topmost surface of the hybrid layer after UV irradiation. Therefore, Ag nano-ink can adhere strongly with glass-like surface.
Development of novel primer material suitable for COP film and Ag nano-ink

Taiki Yamate, Eiko Mieda, Kazuhisa Kumazawa, Hiroshi Suzuki, Motohiro Akazome

Proceedings of the International Display Workshops 3 1781-1784 2015年査読有り

© 2015 Proceedings of the International Display Workshops. All rights reserved. We have developed a unique organic-inorganic hybrid coating agent suitable for a primer which connects Ag nano-ink to COP film. This material forms the glass-like surface on the topmost surface of the hybrid layer after UV irradiation. Therefore, Ag nano-ink can adhere strongly with glass-like surface.