Reduction of styrene compounds by hydrogen iodide

Shoji Matsumoto, Yusuke Fukaya, Motohiro Akazome, Tatsuo Kaiho

Synthetic Communications 1-9 2024年7月5日
Bathochromic Shift of Fluorescence Peak in Dipyrrolo[1,2-a:2′,1′-c]quinoxaline by Introducing Each of Electron-Donating and Electron-Withdrawing Substituent

Shoji Matsumoto, Makoto Takamori, Motohiro Akazome

Molecules 28(7) 2896-2896 2023年3月23日

Development of organic fluorophore is an important theme. Especially, the fluorophores with longer fluorescence peaks are useful to biological probes. One of the methods to change the fluorescence peak is the introduction of substituents. However, opposing characteristics of the substituents lead to different changes in the fluorescence peaks. Furthermore, the introduction of the substituent also affects their electric properties. Thus, if the materials were developed with the substituent effect on the optical and electric properties separately, it will be useful to design the functional materials related to both optical and electric properties. Herein, we investigated the substituent effect of dipyrrolo[1,2-a:2′,1′-c]quinoxalines on fluorescence properties. We synthesized the compounds bearing electron-donating or electron-withdrawing substituents at the benzene ring on dipyrrolo[1,2-a:2′,1′-c]quinoxaline, which would have more direct influence on the optical properties. By introducing each substituent at the 6 position of dipyrrolo[1,2-a:2′,1′-c]quinoxaline, the bathochromic shift was observed in the fluorescence spectra. In the case of fluorine substituent, the change of the fluorescence peak reached was about 19 nm. Using a TDDFT calculation, we explained the reason for such a substituent effect that large on the increment of LUMO energy or decrement of HOMO energy occurred by introducing electron-withdrawing or electron-donating substituents at the 6 position, respectively. The substituent effect on the change of orbital energies is typical although the different characteristics of substituents resulted in the similar tendency about the change of fluorescence peak. Furthermore, with the introduction of phenyl substituents at the 3 and 10 positions, we achieved 40–50 nm longer fluorescence peaks compared with that of the original dipyrrolo[1,2-a:2′,1′-c]quinoxaline.
Relationship between halogen-halogen interaction and electric conductivity in thiazolo[2,3-a]isoquinolin-7-ium triiodides

Shoji Matsumoto, Ryuta Sumida, Motohiro Akazome

Journal of Molecular Structure 1264 133306-133306 2022年9月
Chemoselective reduction of ¡,¢-unsaturated carbonyl and carboxylic compounds by hydrogen iodide

Shoji Matsumoto, Hayato Marumoto, Motohiro Akazome, Yasuhiko Otani, Tatsuo Kaiho

Bulletin of the Chemical Society of Japan 94(2) 590-599 2021年査読有り

The selective reduction of ¡,¢-unsaturated carbonyl compounds was achieved to produce saturated carbonyl compounds with aqueous HI solution. The introduction of an aryl group at an ¡ or ¢ position efficiently facilitated the reduction with good yield. The reaction was applicable to compounds bearing carboxylic acids and halogen atoms. Through the investigation of the reaction mechanism, it was found that Michael-type addition of iodide occurred to produce ¢-iodo compounds followed by the reduction of C-I bond via anionic and radical paths.
Change in the fluorescence of 1,1′-diaryl-2,2′-biimidazoles upon the addition of acid

Shoji Matsumoto, Seigi Tachibana, Motohiro Akazome

Heterocycles 100(10) 1666-1677 2020年査読有り

The optical properties of a series of 1,1′-diaryl-2,2′-biimidazoles were examined. Different transitions were observed in their fluorescence spectra upon changing the electronic properties of the phenyl ring at the C1 and C1′ positions. The presence of a formyl group on the phenyl ring results in fluorescence via a CT transition with a solvent effect. A bathochromic change was observed when HCl was added to a solution of compound bearing a methoxy group in CH2Cl2, whereas a hypsochromic change was observed in compound bearing a formyl group. These observations were attributed to the protonation, which causes a characteristic change in their biimidazole moieties.
Selective synthesis and optical properties of diimidazo[1,2-a:5′,1′-c]quinoxaline derivatives

Shoji Matsumoto, Shunsuke Abe, Motohiro Akazome

Tetrahedron 75(26) 3657-3665 2019年6月28日査読有り

Novel diimidazo[1,2-a:5′,1′-c]quinoxaline derivatives were synthesized by a Pd-catalyzed intramolecular coupling reaction of 1,2-bis(2-iodo-1H-imidazol-1-yl)benzene. This method was applied to the selective introduction of an aryl substituent at the 10 position by the addition of a boronic ester. Moreover, a stepwise introduction of the aryl substituent could be achieved by the further coupling reaction at the 3 position. Focused on the optical properties, a more efficient substituent effect at the 10 position was obtained compared with the analogous structure, diimidazo[1,2-a:2′,1′-c]quinoxaline derivatives. In addition, we revealed that the diimidazo[1,2-a:5′,1′-c]quinoxaline skeleton potentially has an electron-donating character on the optical properties by introducing an electron-withdrawing substituent.
Selective Formation of Internal Olefinic Trimer of α-Methylstyrenes with HI Gas and Ketones

Shoji Matsumoto, Takehisa Oseki, Motohiro Akazome, Yasuhiko Otani

ACS Omega 3(12) 17928-17935 2018年12月20日査読有り

© 2018 American Chemical Society. Reaction of α-methylstyrene in the presence of HI gas and methyl p-tolyl ketone selectively resulted in an internal olefinic trimer. We revealed that the ketones with the stabilization of the protonated state were efficient to give the corresponding trimers, whereas the other ketones gave the usual indane compound. From the investigation for the mechanistic path, we found that the trimer is a kinetic product and that indane is a thermodynamic product.
Exploiting CH/π Interactions in Robust Supramolecular Adhesives

Yamate, Taiki, Fujiwara, Takayuki, Yamaguchi, Toru, Suzuki, Hiroshi, Akazome, Motohiro

Polymer Chemistry 9(32) 4303-4308 2018年8月28日査読有り
Incrementing Stokes Shifts through the Formation of 2,2′-Biimidazoldiium Salts

Shoji Matsumoto, Mei Watanabe, Motohiro Akazome

Organic Letters 20(12) 3613-3617 2018年6月15日査読有り

© 2018 American Chemical Society. The formation of biimidazoldiium structures by the introduction of methyl substituents on the N atoms at the 3 and 3′ positions of 2,2′-biimidazoles led to increments in the Stokes shift of these structures. Based on time-dependent density functional theory (TDDFT) calculations, the imidazolium rings become distorted and the N atoms of the imidazolium rings underwent structural changes through sp2 to sp3 rehybridization in the excited states.
Preparation of chiral 3-oxocycloalkanecarbonitrile and its derivatives by crystallization-induced diastereomer transformation of ketals with chiral 1,2-diphenylethane-1,2-diol

Yohei Yamashita, Daisuke Maki, Shiho Sakurai, Takumi Fuse, Shoji Matsumoto, Motohiro Akazome

RSC Advances 8(57) 32601-32609 2018年査読有り

© 2018 The Royal Society of Chemistry. Chiral 3-oxocycloalkanecarbonitriles were prepared by fractional crystallization and crystallization-induced diastereomer transformation (CIDT) of diastereomeric ketals with (1R,2R)-1,2-diphenylethane-1,2-diol. Investigation of the crystal structures by X-ray diffraction analysis revealed that the difference in hydrogen bonds caused the discrepancy of the solubilities between (R) and (S) diastereomers. Furthermore, CIDT to afford the (R)-diastereomer in good yield (95% yield) and with high diastereoselectivity (97% de) was accomplished, which is the first example of CIDT of neutral compounds via formation of the diastereomeric ketal with (1R,2R)-1,2-diphenylethane-1,2-diol.
Synthesis of iodinated thiazolo[2,3-a]isoquinolinium salts and their crystal structures with/without halogen bond

Shoji Matsumoto, Ryuta Sumida, Sia Er Tan, Motohiro Akazome

Heterocycles 97(2) 755-775 2018年査読有り

© 2018 The Japan Institute of Heterocyclic Chemistry. We investigated the cyclization reaction of 2-(2-(phenylethynyl)-phenyl)thiazoles with I2. A six-membered ring was formed to produce the corresponding thiazolo[2,3-a]isoquinolin-7-ium salts. The counter anions (I− and I3−) varied based on the structure of the thiazole moiety. We also revealed the single-crystal X-ray structures of those thiazolo[2,3-a]isoquinolin-7-ium salts. We discovered that various structures with and without halogen bonds existed, although they were the prospective structures to make “charge-assisted halogen bonds”.
Polyacrylamide-Scaffold Adhesive Bearing Multiple Benzene Rings Forming CH/π Interactions with Polyolefin

Taiki Yamate, Hiroshi Suzuki, Takayuki Fujiwara, Toru Yamaguchi, Motohiro Akazome

Advanced Material Letters 9(7) 526-530 2018年査読有り
Selective Reaction of Benzyl Alcohols with HI Gas: Iodination， Reduction， and Indane Ring Formations

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

Tetrahedron 73(52) 7254-7259 2017年12月28日査読有り
Relationship between Mechanochromic Behavior and CrystalStructures in Donor-π-acceptor Compounds Consisted of Aromatic Rings with Ester Moiety as an Acceptor

Shoji Matsumoto, Jun Moteki, Yuji Ito, Motohiro Akazome

TETRAHEDRON LETTERS 58(36) 3512-3516 2017年9月6日査読有り
Effective Design of Supramolecular Polymer Adhesives Based on Multiple CH/π interactions

Taiki Yamate, Hiroshi Suzuki, Kazuhisa Kumazawa, Takayuki Fujiwara, Toru Yamaguchi, Motohiro Akazome

Molecular Systems Design & Engineering， 2(3) 214-222 2017年8月査読有り
A Practical and Scalable Synthesis of a Glucokinase Activator via Diastereomeric Resolution and Palladium-Catalyzed C-N Coupling Reaction

Yohei Yamashita, Yasuhiro Morinaga, Makoto Kasai, Takao Hashimoto, Yuji Takahama, Atsushi Ohigashi, Satoshi Yonishi, Motohiro Akazome

Organic Process Research and Development 21(3) 346-356 2017年3月17日査読有り

© 2017 American Chemical Society. Here we describe the research and development of a process for the practical synthesis of glucokinase activator (R)-1 as a potential drug for treating type-2 diabetes. The key intermediate, chiral α-arylpropionic acid (R)-2, was synthesized in high diastereomeric excess through the diasteromeric resolution of 7 without the need for a chiral resolving agent. The counterpart 2-aminopyrazine derivative 3 was synthesized using a palladium-catalyzed C-N coupling reaction. This efficient process was demonstrated at the pilot scale and yielded 19.0 kg of (R)-1. Moreover, an epimerization process to obtain (R)-7 from the undesired (S)-7 was developed.
CH/π Interactions for Macroscopic Interfacial Adhesion Design

Taiki Yamate, Kazuhisa Kumazawa, Hiroshi Suzuki, Motohiro Akazome

ACS Macro Letters 5(7) 858-861 2016年7月19日査読有り
Formation of benzimidazoisoquinolinium and benzimidazoisoindolinum cyclic systems by the reaction of 2-(2-alkynylphenyl)benzimidazoles with iodine and iodine-iodine interaction including halogen bonding in their crystal structures

Shoji Matsumoto, Shu Kikuchi, Naoto Norita, Hyuma Masu, Motohiro Akazome

Journal of Organic Chemistry 81(13) 5322-5329 2016年7月1日査読有り

© 2016 American Chemical Society. The reaction of 2-(2-alkynylphenyl)benz[d]imidazoles with molecular iodine constructed 5- and 6-membered rings as novel organic salts in high yield. The constituted number of ring systems was influenced by the substituent at the triple bond: 6-membered rings were formed from compounds bearing aryl substituents, whereas 5-membered ones were obtained from compounds with hydrogen or alkyl substituents. The products were obtained with triiodide as a counteranion; however, compounds with iodide were also obtainable under certain conditions. We also revealed that they had an iodine-iodine interaction included in halogen bonding between an iodo moiety of the cation and a triiodide or iodide of the counteranion. The iodine-iodine interaction was formed with greater preference than the electrostatic interaction between the cationic atom and triiodide or iodide.
HI Gas as a Reagent for α-Alkylation Reaction with Two Ketone Molecules

Shoji Matsumoto, Seigo Koitabashi, Yasuhiko Otani, Motohiro Akazome

TETRAHEDRON LETTERS 56(29) 4320-4323 2015年6月14日査読有り
Systematic Investigation of Fluorescence Properties of Symmetric and Asymmetric Diazolo[1，2-a:2′，1′-c]quinoxaline Derivatives

Shoji Matsumoto, Keisuke Sakamoto, Motohiro Akazome

Heterocycles 91(4) 795-814 2015年査読有り
Binding of acetylcholine and quaternary ammonium compounds to a C <inf>3</inf>-symmetric bowl-shaped tripeptide of 2-(3-aminophenoxy)propanoic acids acting as a ditopic receptor

Motohiro Akazome, Norihiro Hamada, Koji Takagi, Daisuke Yagyu, Shoji Matsumoto

Tetrahedron Letters 55(14) 2226-2229 2014年4月査読有り

The new tripeptide reported here is composed of (R)-2-(3-aminophenoxy) propionic acid and is a bowl-shaped receptor that simultaneously binds both cations and anions of acetylcholine chloride and benzyltrimethylammonium compounds. An intriguing conformational change of the host was observed in the complexation of the ionic pair, where anion-induced flipping of the amide group on the macrocycle occurred. © 2014 Elsevier Ltd. All rights reserved.
Formation of benzo[c]thiophen-1-aminium iodide by the reaction of o-alkynylbenzothioamide with iodine

Shoji Matsumoto, Daiki Takada, Hirokazu Kageyama, Motohiro Akazome

Tetrahedron Letters 55(5) 1082-1085 2014年1月29日査読有り

Reaction of o-alkynylbenzothioamide with molecular iodine was investigated. Unique benzo[c]thiophen-1-aminium iodide was obtained when the tertiary thioamide was used as a reactant. The reaction proceeded efficiently in less polar solvent, whereas the corresponding product was also obtained in a polar solvent. Single crystal X-ray analysis revealed that the benzo[c]thiophen-1- aminium structure possesses a resonance structure in N-C-S bond. Its stabilization shows a clear difference in the result from the reaction of amide analogue with iodine to give no stable compound. © 2013 Elsevier Ltd. All rights reserved.
SYNTHESIS AND OPTICAL PROPERTIES OF 2，2 '-BIIMIDAZOLE AND BENZO[d]IMIDAZOLE DERIVATIVES: CHANGING pi-CONJUGATION BY PHOTOEXCITATION

Matsumoto, Shoji, Zhao, Yu, Akazome, Motohiro

HETEROCYCLES 88(1) 261-273 2014年査読有り
Fluorescence of Diimidazo[1，2-a:2 '，1 '-c]quinoxalinium Salts Under Various Conditions

Matsumoto, Shoji, Abe, Hajime, Akazome, Motohiro

JOURNAL OF ORGANIC CHEMISTRY 78(6) 2397-2404 2013年3月15日査読有り
α-diketone formation accompanied by oxidation of sulfur functional group by the reaction of o-alkynylarenesulfoxide with iodine

Shoji Matsumoto, Hiroyuki Shibata, Motohiro Akazome

Journal of Organic Chemistry 78(4) 1650-1654 2013年2月15日査読有り

The reaction of o-alkynylarenesulfoxide with iodine was investigated in detail, revealing functionalities of the formation of α-diketones with sulfenyl, sulfinyl, and sulfonyl. Additives can change the ratio of products to give medium-to-excellent yields. Results show that water is taken into only sulfonyl compound and that other oxygen atoms constructed in the products are presumably derived from sulfoxide of the starting material and molecular oxygen. © 2013 American Chemical Society.
Enantioselective inclusion of amide guests into a chiral N，N '-ditrityl amino amide host to compensate the loss of hydrogen bonds broken by installation of trityl groups

Megumi, Ken, Yokota, Shohei, Matsumoto, Shoji, Akazome, Motohiro

TETRAHEDRON LETTERS 54(7) 707-710 2013年2月13日査読有り
Design and evaluation of salts between N-trityl amino acid and tert -butylamine as inclusion crystals of alcohols

Ken Megumi, Fara Nadiah Binti Mohd Arif, Shoji Matsumoto, Motohiro Akazome

Crystal Growth and Design 12(11) 5680-5685 2012年11月7日査読有り

Salts between N-trityl amino acids (Ala, Val, Leu, Ile, Phe, and phenylglycine) and tert-butylamine are examined in terms of inclusion ability for alcohols. An X-ray crystallographic study elucidated the column structures, hydrogen-bond network, and phenyl-phenyl interactions. It also found that tert-butylammonium N-trityl phenylalanate was superior to other salts of amino acids at including several alkyl alcohols. When the salt included 1-chloro-2-propanol as a guest alcohol, the enatioselectivity of inclusion reached up to 69% ee (S-form). © 2012 American Chemical Society.
Synthesis and fluorescence properties of N-methyl-1，2-dihyroquinoline-3-carboxylate derivatives: light-emitting compounds in organic solvent， in neat form， and in water

Matsumoto, Shoji, Mori, Takahiro, Akazome, Motohiro

RSC ADVANCES 2(8) 3379-3386 2012年4月査読有り
Utilization of Carboxylated 1，3-Indandione as an Electron Acceptor in Dye-Sensitized Solar Cells

Matsumoto, Shoji, Aoki, Tatsuro, Suzuki, Tasutaka, Akazome, Motohiro, Betto, Atsushi, Suda, Yasumasa

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 85(12) 1329-1331 2012年査読有り
Novel formation of diimidazo[1,2-a:2′,1′-c]quinoxaline derivatives and their optical properties

Shoji Matsumoto, Erdenebolor Batmunkh, Motohiro Akazome, Yoshiyuki Takata, Michiko Tamano

Organic and Biomolecular Chemistry 9(17) 5941-5944 2011年9月7日査読有り

Reaction of 1,2-di(imidazolyl)benzene treated with n-BuLi proceeded to give diimidazo[1,2-a:2′,1′-c]quinoxaline in the presence of iodine or Pd(PPh 3) 4. Blue fluorescence was observed from 3,10-diarylated diimidazoquinoxalines with high quantum yield. They were also applied to organic light-emitting devices as emitters, in which the diphenyl derivative emits a nearly pure blue light. © 2011 The Royal Society of Chemistry.
Synthesis and C<inf>2</inf>-symmetric structure of a cyclotetrapeptide composed of anthranilic acid and leucine

Motohiro Akazome, Masashi Enzu, Koji Takagi, Shoji Matsumoto

Chirality 23(7) 568-573 2011年8月査読有り

A chiral cyclotetrapeptide (1) was synthesized from 2-nitrobenzoic acid and leucine. A single-crystal X-ray of the compound revealed a C 2-symmetric bowl-shaped structure. The cyclic compound had a unique hydrogen-bonding network composed of three-centered hydrogen bonds and bifurcated hydrogen bonds between NH and CO of anthranilic residue. The NMR spectra and molecular modeling of 1 also suggested the chiral bowl structure. © 2011 Wiley-Liss, Inc.
Inclusion of aliphatic alcohols in pockets of (S)-threonyl-(S)- phenylglycine using grinding method

Motohiro Akazome, Shusaku Toma, Tatsunori Horiguchi, Ken Megumi, Shoji Matsumoto

Tetrahedron 67(16) 2844-2848 2011年4月査読有り

Inclusion compounds of a dipeptide, (S)-threonyl-(S)-phenylglycine (Thr-Phg), with several aliphatic alcohols were easily prepared by grinding them in a mortar. Thr-Phg molecules arranged in antiparallel to construct a sheet, and guest alcohols were accommodated in a chiral pocket between the sheets. 3-Butyn-2-ol and 2-butanol were included with moderate enantioselectivity, 57% ee (R) and 49% ee (R), respectively. The role of the hydroxy group of Thr-Phg is not only to construct the unique pocket but also to capture guest alcohols by hydrogen bonding. © 2011 Elsevier Ltd. All rights reserved.
Synthesis of a chiral C<inf>3</inf>-symmetric bowl-shaped cyclohexapeptide composed of anthranilic acid and leucine

Motohiro Akazome, Masashi Enzu, Yohei Goto, Shoji Matsumoto

Heterocycles 82(2) 1645-1656 2010年2月28日査読有り

A chiral C3-syrnmetric bowl-shaped cyclohexapeptide (1), composed of anthranilic acid (2-aminobenzoic acid) and α-amino acid in an alternating sequence, was synthesized from 2-nitrobenzoic acid and leucine. The 1H and 13CNMR spectra of 1 suggest a chiral C 3-symmetric bowl-shaped structure. Molecular mechanic calculation revealed that the cyclohexapeptide becomes a bowl-shaped structure when all three α-amino acid components have homochiral side chains. © The Japan Institute of Heterocyclic Chemistry.
Predominant (S)-enantioselective inclusion of aryl methyl sulfoxides by (S)-isoleucyl-(S)-phenylglycines

Motohiro Akazome, Ai Doba, Shoji Matsumoto, Katsuyuki Ogura

Journal of Organic Chemistry 75(3) 660-665 2010年2月5日査読有り

(Figure Presented) In terms of chiral recognition for racemic aryl methyl sulfoxides in the solid state, three kinds of crystalline (S)-alkylglycyl-(S)- phenylglycines were examined as potential dipeptides host molecules. When (S)-alanyl-(S)-phenylglycines [(S,S)-Ala-Phg] crystallized with aryl methyl sulfoxides, the stereochemistry of preferentially included sulfoxides depended on the individual shapes of the sulfoxides and the enantiomeric excess was relatively low. Although (S)-leucyl-(S)-phenylglycines [(S,S)-Leu-Phg] and (S)-isoleucyl-(S)-phenylglycines [(S,S)-Ile-Phg] mainly included the S-form of aryl methyl sulfoxides, the enantiomeric recognition of (S,S)-Ile-Phg was superior to that of (S,S)-Leu-Phg. Single-crystal X-ray analysis of these inclusion compounds revealed that the dipeptide molecules self-assembled to form layer structures and included sulfoxides between these layers through hydrogen bonding between the proton of +NH3 and the oxygen of the sulfoxide. Besides these host-guest interactions, the phenyl groups of the sulfoxides interacted with each other through the phenyl-phenyl interaction. Two adjacent homochiral sulfoxides make a pair having a 2-fold screw axis along the channel cavity. Thus, the self-recognition of sulfoxides made 21 helical column structures and had high enantioselectivity. © 2010 American Chemical Society.
Formation of 1，2-Dihydroquinoline-3-carboxylic Acid Derivatives from Methyl 3-(Arylamino)acrylates with Hydrogen Iodide

Matsumoto S, Mori T, Akazome M

Synthesis (21) 3615-3622 2010年査読有り
Novel Formation of Dipyrolo- and Diindolo[1，2-a:2’，1’-c]quinoxaline Derivatives and Their Optical Properties

赤染元浩

Heterocycles 80(1) 645-656 2010年1月1日査読有り
A cyclic trimer of 2-(2-aminophenoxy)propionic acid with a bowl-shaped structure

Motohiro Akazome, Junpei Sukegawa, Yohei Goto, Shoji Matsumoto

Tetrahedron Letters 50(38) 5382-5385 2009年9月23日査読有り

A cyclic trimer of (R)-2-(2-aminophenoxy)propanoic acid, a δ-amino acid analogue, was synthesized. Molecular mechanics calculations on the cyclic trimer predicted that a concave network of sequential hydrogen bonds forms a C3-symmetric bowl-shaped structure. Evidence for this conformation was found in the NMR spectra of the trimer in d-chloroform. Although the single-crystal structure of the cyclic trimer indicates that chloroform could be included in the bowl-shaped structure, the conformation was not C3-symmetric and the hydrogen bonding network was of a different mode. These different conformations between solid and solution were reasonably clear from IR spectra. © 2009 Elsevier Ltd. All rights reserved.
Electric conductivity in the complex of mesoionic anhydro-3-hydroxythiazolo[3,2-a]pyridinium hydroxide with iodine

Shoji Matsumoto, Kazuto Kimura, Takeru Sano, Motohiro Akazome, Katsuyuki Ogura

Journal of Photopolymer Science and Technology 22(5) 677-678 2009年9月査読有り
Synthesis and physical properties of various organic dyes derived from a single core skeleton, 1,2-dihydroindol-3-one

Shoji Matsumoto, Daisuke Samata, Motohiro Akazome, Katsuyuki Ogura

Tetrahedron Letters 50(1) 111-114 2009年1月7日査読有り

Various organic dyes were synthesized from 1,2-dihydroindol-3-one analogue via Robinson ring annulation, which proceeded efficiently using DBU as a base to give the π-expanded compounds. These compounds exhibited longer Stokes shifts (over 100 nm) than the 1,2-dihydroindol-3-ones (50-80 nm). Emission peaks of the obtained materials covered the 440-640 nm range. © 2008 Elsevier Ltd. All rights reserved.
Induced helix of 2-(2-aminophenoxy)alkanoic acid oligomers as a δ-peptidomimetic foldamer

AKAZOME Motohiro, ISHII Yuichi, NIREKI Tatsuya, OGURA Katsuyuki

Tetrahedron Letters 49(28) 4430-4433 2008年7月7日査読有り
Inclusion compounds of l,d-dipeptide with small sulfoxides: flexible sheet structure of (S)-phenylglycyl-(R)-phenylglycine

Motohiro Akazome, Atsushi Hirabayashi, Kyoko Senda, Katsuyuki Ogura

Tetrahedron 63(40) 9933-9938 2007年10月1日査読有り

A heterochiral l,d-dipeptide, (S)-phenylglycyl-(R)-phenylglycine (SR-1), formed inclusion compounds with some small dialkyl sulfoxides. By their single-crystal X-ray analyses, we observed monolayer structures, where SR-1 molecules are arranged in parallel to construct a wavy sheet. The sulfoxides were accommodated in a channel cavity between the monolayers of SR-1 by hydrogen bonding with +NH3 of SR-1. Notably, the sheet of SR-1 is so flexible to change its wavy degree in response to the volume of the included sulfoxides. Furthermore, we could analyze the structure of crystalline SR-1 without any sulfoxide, which has a bilayer structure. © 2007.
Formation of metal-lustrous organic crystals from 2-aryl-1-(4- methoxyphenyl)-5-(5-tricyanoethenyl-2-thienyl)pyrroles

Katsuyuki Ogura, Kenji Ooshima, Motohiro Akazome, Shoji Matsumoto

Tetrahedron 62(11) 2484-2491 2006年3月13日査読有り

Various 2-aryl-1-(4-methoxyphenyl)-5-(5-tricyanoethenyl-2-thienyl)pyrroles (3) were synthesized. When the 2-aryl group of 3 is phenyl, 4-tolyl, and 4-methoxyphenyl, organic crystals with greenish yellow metallic luster are formed. In contrast, a 2-(4-fluorophenyl) derivative of 3 gives gold-like lustrous crystals. The relation of their crystal structures with the appearance of metallic color is mentioned. © 2006 Elsevier Ltd. All rights reserved.
Greenish metal-lustrous organic crystals formed from 1-aryl-2-(2-thienyl)- 5-(5-tricyanoethenyl-2-furyl)pyrroles

Katsuyuki Ogura, Kenji Ooshima, Motohiro Akazome, Shoji Matsumoto

Tetrahedron 62(10) 2413-2419 2006年3月6日査読有り

On the treatment of 1-aryl-2-(2-furyl)-5-(2-thienyl)pyrroles with tetracyanoethylene, 1-aryl-2-(2-thienyl)-5-(5-tricyanoethenyl-2-furyl)pyrroles were produced. These compounds formed crystals with greenish metallic luster. In their solid-state UV-vis-NIR diffuse reflection-absorption spectra, absorption band corresponding to metallic reflection spreads in the range of 550-900 nm. Furthermore, strong absorption appeared below 520-540 nm. This absorption results in the appearance of green color. Single-crystal X-ray crystallographic analysis revealed the crystal structure of 1-(4-methoxyphenyl)-2-(2-thienyl)-5- (5-tricyanoethenyl-2-furyl)pyrrole (2c). The distinct features of the crystal structure are as follows: (1) the thiophene-pyrrole-furan-tricyanoethenyl π-system is approximately flat; (2) the conformational relation between the pyrrole ring and the furan ring is anti, that is, these rings are pointing in opposite directions and the dihedral angle of N-C-C-O=180°; (3) as a result, the tricyanoethenyl group is far from the 4-methoxyphenyl group; (4) the molecules of 2c are arranged in a ribbon structure; (5) the ribbons are assembled side-by-side to form a terraced layer; (6) the layers stack so that the π-orbitals of 2c become close to each other. © 2005 Elsevier Ltd. All rights reserved.
Novel Synthesis of α-Trifluoromethylated α-Amino Acid Derivatives from γ-Hydroxy-α-fluoro-α-trifuluoromethyl Carboxamides

OGU K, MATSUMOTO S, AKAZOME M, OGURA K

Organic Letters 7(4) 589-592 2005年2月17日査読有り
Molecular recognition of l-leucyl-l-alanine: Enantioselective inclusion of alkyl methyl sulfoxides

Motohiro Akazome, Atsushi Hirabayashi, Kousuke Takaoka, Satoru Nomura, Katsuyuki Ogura

Tetrahedron 61(5) 1107-1113 2005年1月31日査読有り

A simple aliphatic dipeptide, l-leucyl-l-alanine (Leu-Ala), includes several alkyl methyl sulfoxides enantioselectively to form inclusion crystals. From single-crystal X-ray analyses of three inclusion compounds of dimethyl sulfoxide (DMSO), isobutyl methyl sulfoxide, and benzyl methyl sulfoxide, it was elucidated that Leu-Ala molecules self-assemble to form layer structures and the sulfoxides are included via hydrogen bonding in a cavity between these layers. The inclusion cavity has methyl group and isobutyl group at its each side, and the guest sulfoxide is placed in such a manner that its methyl group faces toward the methyl of the Leu-Ala cavity. When the alkyl group of the sulfoxide is comparably large, it is located in the residual space of the cavity to attain effective crystal packing. Thus, the sulfoxides having a comparably large group such as isobutyl, butyl, and benzyl are included with a high (R)-enantioselectivity in Leu-Ala crystals. © 2004 Elsevier Ltd. All rights reserved.
Enantioselective inclusion of (R)-phenylglycyl-(R)-phenylglycine with benzyl methyl sulfoxides

Motohiro Akazome, Atsushi Hirabayashi, Katsuyuki Ogura

Tetrahedron 60(52) 12085-12093 2004年12月20日査読有り

A crystalline dipeptide, (R)-phenylglycyl-(R)-phenylglycine (RR-1), recognized p-halobenzyl methyl sulfoxides with high R-enantioselectivity (86-99% ee) to form inclusion compounds. The single-crystal X-ray analyses showed that RR-1 molecules are arranged in parallel and zigzags via hydrogen bonding to construct a pleated sheet. The guest molecules that form hydrogen bond with +NH 3 of RR-1 are accommodated in the channel cavity between the layers. In contrast to the inclusion crystals of parent benzyl methyl sulfoxide, in which a rectangular cavity is formed, the cavity including p-halobenzyl methyl sulfoxides becomes rhomboidal. We also examine the guest exchange in these inclusion compounds and it was found that the guest exchanges occur when the host structure changes. Graphical Abstract. © 2004 Published by Elsevier Ltd.
Diastereoselective formation of 2-fluoro-2-trifluoromethyl-3, 4-alkadienamides from propargyl alcohols and hexafluoropropene-diethylamine adduct (PPDA)

Kenichi Ogu, Motohiro Akazome, Katsuyuki Ogura

Journal of Fluorine Chemistry 125(3) 429-438 2004年3月1日査読有り

Treatment of propargyl alcohols (1) with hexafluoropropene-diethylamine adduct (PPDA) affords N,N-diethyl-2-fluoro-2-trifluoromethyl-3,4-alkadienamides (2) that are produced by the Claisen rearrangement of intermediary 2-alkynyl 1-(N,N-diethylamino)-2,3,3,3-tetrafluoro-1-propenyl ethers. Starting from propargyl alcohols bearing a triple bond at the terminal position, the corresponding products (2) were formed with a high stereoselectivity. © 2003 Elsevier B.V. All rights reserved.
Formation of Gold-like Metal-lustrous Inclusion Crystals from 1-Phenyl-2,5-bis[5-(tricyanoethenyl)-5-thienyl]-pyrrole Host and an Electron-donating Aromatic Guesｔｓ

OGURA K, ZHAO R, MIZUOKA T, AKAZOME M, MATSUMOTO S

Organic&Biomolecular Chemistry 1(21) 3845-3850 2003年11月7日査読有り
A novel reaction of allylic alcohols with hexafluoropropene-diethylamine adduct (PPDA) to form 2-fluoro-2-trifluoromethyl-4-alkenamide

Ken Ichi Ogu, Motohiro Akazome, Katsuyuki Ogura

Journal of Fluorine Chemistry 124(1) 69-80 2003年11月1日査読有り

Treatment of allylic alcohols with hexafluoropropene-diethylamine adduct (PPDA) afforded N,N-diethyl-2-fluoro-2-trifluoromethyl-4- alkenamides which were formed by the Claisen rearrangement of intermediary 2-alkenyl-1-diethylamino-2,3,3,3-tetrafluoro-1-propenyl ethers. Although (E)-allylic alcohols gave two diastereomeric products in about 1:1 ratio, (Z)-allylic alcohols gave the corresponding product as a single diastereomer. © 2003 Elsevier B.V. All rights reserved.
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.

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.