Kyushu University Academic Staff Educational and Research Activities Database
List of Papers
Junji Tanaka Last modified date:2019.06.28

Assistant Professor / Department of Fundamental Organic Chemistry / Institute for Materials Chemistry and Engineering


Papers
1. Md Monarul Islam, Xing Feng, Shofiur Rahman, Paris E. Georghiou, Taisuke Matsumoto, Junji Tanaka, Abdullah Alodhayb, Carl Redshaw, Takehiko Yamato, Synthesis, Structures and Lewis-Acid-Induced Isomerization of 8-Methoxy[2.2]metaparacyclophanes and a DFT Study, ChemistrySelect, 10.1002/slct.201900190, 4, 13, 3630-3635, 2019.04, Methyl substituted 8-methoxy[2.2]MPCPs 8 a–b were obtained via thiacyclophane and its oxidized products. Lewis acid-catalyzed (AlCl
3
-MeNO
2
) reactions of 5-tert-butyl-8-methoxy-12,13,15,16-tetramethyl[2.2]MPCP 8 b under various conditions led to transannular cyclization and isomerization reactions, affording the considerably less-strained 5-tert-butyl-8-methoxy[2.2]MPCP 9, 5-tert-butyl-8-hydroxy-14,16,17,18-tetramethyl[2.2]metacyclophane 10 and pyrene derivatives 11 and 12. However,on prolonging the reaction time to 3 h for 8 b, the major product is 5-tert-butyl-8-hydroxy[2.2]MPCP 10. These reactions are strongly affected by the size and properties of the C-8 substitutents as well as the methyl substitutents on the para-linked benzene rings, which increase the strain in the molecules. The
1
H NMR spectra and X-ray crystallographic analysis of 8 b revealed that it adopts a syn-conformation both in solution and in the solid state..
2. Thamina Akther, Md Monarul Islam, Shofiur Rahman, Paris E. Georghiou, Taisuke Matsumoto, Junji Tanaka, Pierre Thuéry, Carl Redshaw, Takehiko Yamato, Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes, ChemistrySelect, 10.1002/slct.201600670, 1, 13, 3594-3600, 2016.01, A series of 1,2-dimethyl[2.10]metacyclophan-1-enes (MCP-1-enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 3 was synthesized by a Grignard coupling reaction, Friedel-Crafts acylation reactions and McMurry coupling reaction from 1,10-dibromodecane. The formation of 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X-ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21-diformyl-4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 6 has been prepared from 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X-ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti-conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds..
3. Xing Feng, Nobuyuki Seto, Chuan Zeng Wang, Taisuke Matsumoto, Junji Tanaka, Xian Fu Wei, Mark R.J. Elsegood, Lynne Horsburgh, Carl Redshaw, Takehiko Yamato, Extended π-Conjugated Pyrene Derivatives
Structural, Photophysical and Electrochemical Properties, ChemistrySelect, 10.1002/slct.201600598, 1, 9, 1926-1932, 2016.01, This article presents a set of extended π-conjugated pyrene derivatives, namely 1,3-di(arylethynyl)-7-tert-butylpyrenes, which were synthesized by a Pd-catalyzed Sonogashira coupling reaction of 1,3-dibromo-7-tert-butylpyrenes with the corresponding arylethynyl group in good yields. Despite the presence of the tert-butyl group located at the 7-position of pyrene, X-ray crystallographic analyses show that the planarity of the Y-shaped molecules still exhibits strong face-to-face π-π stacking in the solid state; all of the compounds exhibit blue or green emission with high quantum yields (QYs) in dichloromethane. DFT calculations and electrochemistry revealed that this category of compound possesses hole-transporting characteristics. In addition, with strong electron-donating (-N(CH3)2) or electron-withdrawing (-CHO) groups in 2 d or 2 f, these molecules displayed efficient intramolecular charge-transfer (ICT) emissions with solvatochromic shifts from blue to yellow (green) on increasing the solvent polarity. Furthermore, the compounds 2 d and 2 f possess strong CT characteristics..
4. Md Monarul Islam, Thamina Akther, Shofiur Rahman, Paris E. Georghiou, Taisuke Matsumoto, Junji Tanaka, Carl Redshaw, Takehiko Yamato, Synthesis, Conformational Properties and DFT Computational Studies of Polymethyl-Substituted [3.3]Metacyclophanes, ChemistrySelect, 10.1002/slct.201701243, 2, 24, 7255-7262, 2017.01, Polymethyl substituted [3.3]metacyclophanes (MCPs) 4 a–d, were synthesized by the TosMIC coupling method followed by Wolff–Kishner reduction of the corresponding polymethyl-substituted [3.3]MCP-2,11-diones (3 a–d). 1H NMR spectroscopy reveals that both 5,6,7,14,16-pentamethyl[3.3]MCP-2,11-diones (3 a and 3 b) undergo conformational changes relative to the NMR time scale in solution at room temperature but that the anti conformer is preferred. Reduced 5,6,7,14,16-pentamethyl[3.3]MCP (4 a and 4 b) adopt fixed syn–conformations in solution at room temperature. X-ray analysis showed that in the solid state, 5,6,7,14,15,16-hexamethyl[3.3]MCP-2,11-dione 3 a adopts the anti-conformation and reduced 5,6,7,14,16-pentamethyl[3.3]MCP-2,11-diones 4 b adopts a syn-(chair-chair) conformation. A series of electrophilic substitution reactions such as formylation, acetylation and nitration were carried out with 5,6,7,14,16-pentamethyl[3.3]MCP 4 b to study their conformational isomers. The formyl, acetyl and nitro derivatives of 5,6,7,14,16-pentamethyl[3.3]MCP are fixed to adopt syn-conformations in solution at room temperature. The conformational isomers of the metacyclophanes and derivatives obtained from density functional theory (DFT) methods were used to estimate the total energies and energy minimized structures of the different conformations..
5. Thamina Akther, Md Monarul Islam, Shofiur Rahman, Paris E. Georghiou, Taisuke Matsumoto, Junji Tanaka, Carl Redshaw, Takehiko Yamato, Synthesis and conformations of [2.n]metacyclophan-1-ene epoxides and their conversion to [n.1]metacyclophanes, Organic and Biomolecular Chemistry, 10.1039/c7ob00400a, 15, 16, 3519-3527, 2017.01, A series of syn- and anti-[2.n]metacyclophan-1-enes have been prepared in good yields by McMurry cyclizations of 1,n-bis(5-tert-butyl-3-formyl-2-methoxyphenyl)alkanes. Significantly, acid catalyzed rearrangements of [2.n]metacyclophan-1-enes afforded [n.1]metacyclophanes in good yield. The ratios of the products are strongly regulated by the number of methylene bridges present. The percentages of the rearrangement products increase with increasing length of the carbon bridges. Characterization and the conformational studies of these products are described. Single crystal X-ray analysis revealed the adoption of syn- and anti-conformations. DFT calculations were carried out to estimate the energy-minimized structures of the synthesized metacyclophanes..
6. Thamina Akther, Md Monarul Islam, Taisuke Matsumoto, Junji Tanaka, Pierre Thu�ry, Carl Redshaw, Takehiko Yamato, Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes, Liebigs Annalen der Chemie, 10.1002/ejoc.201601647, 2017, 13, 1721-1726, 2017.01, Bromination of 5,21-di-tert-butyl-8,24-dimethoxy-1,2-dimethyl[2.10]metacyclophan-1-ene (MCP-1-ene; 1) with benzyltrimethylammonium tribromide exclusively afforded 1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene (2). Debromination of 2 with Zn and AcOH in CH2Cl2 solution at room temperature for 24 h produced dimethylene[2.10]MCP 7 in 92 % yield, which is a stable solid compound. Compound 7 was treated with dimethyl acetylenedicarboxylate (DMAD) to provide 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate (8) in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged dimethoxy[2.10]MCP-4′,5′-dimethylcarboxylate 9, possessing C1 symmetry, by aromatization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). A new type of N-phenyl-maleimide substituted 1,2-(3′,6′-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4′,5′-N-phenylmaleimide 10 was also synthesized from 7 through treatment with N-phenylmaleimide in toluene at 110 �C followed by aromatization with DDQ. Single-crystal X-ray analysis of 9 revealed the formation of a syn-isomer..
7. Chuan Zeng Wang, Jung Hee Do, Tahmina Akther, Xing Feng, Taisuke Matsumoto, Junji Tanaka, Carl Redshaw, Takehiko Yamato, Synthesis and fluorescence emission properties of D-π-D monomers based on dithieno[3,2-b
2′,3′-d]thiophene, Journal of Luminescence, 10.1016/j.jlumin.2017.04.060, 188, 388-393, 2017.08, We herein present four highly fluorescent and stable D-π-D monomers (2), which were designed and synthesized using different types of aryl substituent as the donor via a Suzuki-Miyaura coupling reaction. We have studied these four symmetrical chromophores by UV–vis absorption and fluorescence emission spectroscopy both in solution and the solid state. This research shows that the introduction of the aryl groups can effectively reduced the HOMO-LUMO gap of thiophene chromophore resulting in a shift of the wavelength of the absorption and fluorescence emission. The notable optical features of their solid-state powders also exhibited a distinct red-shift in comparison with the emissions of their dilute solutions. These results combined with the theoretical calculations (B3LYP/6–31G*) indicate that these systems are promising candidates in the fabrication of organic electroluminescence devices..
8. Thamina Akther, Md Monarul Islam, Taisuke Matsumoto, Junji Tanaka, Pierre Thuéry, Carl Redshaw, Takehiko Yamato, Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane, Tetrahedron, 10.1016/j.tet.2017.11.075, 74, 2, 329-335, 2018.01, The reductive coupling reaction of 1,4-bis(3-acetyl-5-tert-butyl-2-methoxyphenyl)butane 3 was carried out using TiCl4-Zn in pyridine followed by a McMurry coupling reaction to afford the compounds anti and syn 1,2-dimethyl[2.4]MCP-1-ene 4. Bromination of 4 with BTMA-Br3 in dry CH2Cl2 afforded the interesting compound 1,2-bis-(bromomethyl)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-1-ene 6 and consecutive debromination with Zn and AcOH in CH2Cl2 solution afforded the stable solid 5,15-di-tert-butyl-8,18-dimethoxy-1,2-dimethylene[2.4]MCP 7 in 89% yield. Compound 7 was conveniently employed in a Diels–Alder reaction with dimethyl acetylenedicarboxylate (DMAD) to provide 2-(3′,6′-dihydrobenzo)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-4′,5′-dimethylcarboxylate 8 in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged compound [2.4]MCP 9 by aromatization. The chirality of the two conformers was characterized by circular dichroism (CD) spectra of the separated enantiomer which are perfect mirror images of each other..
9. Akther, Thamina, Islam, Md Monarul, Matsumoto, Taisuke, Junji Tanaka, Junji; Feng, Xing, Redshaw, Carl, Yamato, Takehiko, Demethylation of 5,n-di-tert-butyl-8,n-dimethoxy[2.n] metacyclophane-1-ynes with BBr3 to afford novel [n] benzofuranophanes, JOURNAL OF MOLECULAR STRUCTURE, 10.1016/j.molstruc.2016.05.054, 1122, 247-255, 2016.10.
10. Islam, Md Monarul, Akther, Thamina, Ikejiri, Yusuke, Matsumoto, Taisuke, Junji Tanaka, Rahman, Shofiur, Georghiou, Paris E, Hughes, David L., Redshaw, Carl, Yamato, Takehiko, Synthesis, structural properties, electrophilic substitution reactions and DFT computational studies of calix[3]benzofurans, RSC ADVANCES, 10.1039/c6ra06219a, 6, 56, 50808-50817.
11. Islam, M. Monarul, Hirotsugu, Tomiyasu, Matsumoto, Taisuke, Junji Tanaka, Yamato, Takehiko, Synthesis and conformational studies of 9-benzyloxy-18-substituted [3.3]metacyclophanes, CANADIAN JOURNAL OF CHEMISTRY, 10.1139/cjc-2015-0174, 93, 11, 1161-1168, 2015.11.
12. Islam, Md Monarul, Hirotsugu, Tomiyasu, Thuery, Pierre, Matsumoto, Taisuke, Junji Tanaka, Elsegood, Mark R. J, Redshaw, Carl, Yamato, Takehiko, Synthesis and conformational studies of calixarene analogue chiral [3.3.1]metacyclophanes, JOURNAL OF MOLECULAR STRUCTURE, 10.1016/j.molstruc.2015.05.036, 1098, 47-54, 2015.10.
13. Hu, Jian-Yong, Feng, Xing, Seto, Nobuyuki, Iwanaga, Fumitaka, Era, Masanao, Matsumoto, Taisuke, Junji Tanaka, Takehiko Yamato, Synthesis, crystal structure and photophysical properties of 5-mono- and 5,9-bis-(arylethynyl)-functionalized pyrenes, JOURNAL OF LUMINESCENCE, 10.1016/j.jlumin.2013.03.014, 141, 111-120, 2013.09.
14. Jian-Yong Hu, Arjun Paudel, Nobuyuki Seto, Xing Feng, Masanao Era, Taisuke Matsumoto, Junji Tanaka, Mark R. J. Elsegood, Carl Redshaw, Takehiko Yamato, Pyrene-cored blue-light emitting [4]helicenes: synthesis, crystal structures, and photophysical properties, Organic & Biomolecular Chemistry, 10.1039/c3ob27320b, 11, 2186-2197, 2013.01, The synthesis, crystal structures and photophysical properties of two types of pyrene-cored blue-light
emitting [4]helicenes (7 and 9) are reported. The chemical structures of all synthesized compounds were
fully confirmed by 1H and 13C NMR spectra, mass spectroscopy as well as elemental analysis. Singlecrystal
X-ray analysis of these [4]helicenes revealed that there are two types of laterally naphthalene
annulated helical architectures, which are clearly influenced by different R substituents. The photophysical
properties of the [4]helicenes (7 and 9) were fully investigated in both solutions and films, along with
the pre-cyclization products, 4,9- and 4,10-bis(phenylethenyl)pyrenes (6 and 8). Notable optical features
were obtained in these compounds, which make them promising candidates for several important applications
in modern electronic and optoelectronic devices, such as blue emitters in organic light-emitting
devices (OLEDs), or as models for further exploring the development of a new generation of organic
materials based on pyrene..
15. Jian-YongHu, XingFeng, NobuyukiSeto, FumitakaIwanaga, MasanaoEra, TaisukeMatsumoto, Junji Tanaka, TakehikoYamato, Synthesis, crystalstructureandphotophysicalproperties of 5-mono-and5,9-bis-(arylethynyl)-functionalizedpyrenes, Journal ofLuminescence, 141, 111-120, 2013.03, 7-tert-Butyl-1,3-dimethylpyrene5-carbaldehydeand7-tert-butyl-1,3-dimethylpyrene5,9-dicarbalde-
hydewereconvertedtothecorresponding(4-methoxyphenylethynyl)pyrenesbytheWittigreaction
with 4-methoxyphenylmethylphosphoniumylidefollowedbybrominationanddehydrobromination.
Single-crystal X-rayanalysisof7-tert-butyl-5-(4-methoxyphenylethynyl)-1,3-dimethylpyrenerevealed
that thereisa1-D,slipped,face-to-facemotifwithoff-set,head-to-tailstackedcolumns,whichare
clearlyinfluenced bythesingle,bulky, tert-butyl groupinthepyreneringatthe7-position.Detailed
studies onphotophysicalpropertiesandelectrochemicalcharacteristicsinsolutionsstronglyindicate
that theymightbepromisingcandidatesfororganicoptoelectronicapplications,suchasorganiclight-
emitting devices(OLEDs)orasmodelsforinvestigatingthe fluorescent structure-propertyrelationshipof
the alkynyl-functionalizedpyrenederivatives..
16. Kaoru Takamura, Hisami Matsuo, Ayana Tanaka, Junji Tanaka, Tsutomu Fukuda, Fumito Ishibashi, Masatomo Iwao, Total synthesis of the marine natural products lukianols A and B, Tetrahedron, 69, 2782-2788, 2013.04, Total synthesis of the pyrrolic marine natural products lukianols A (1) and B (2) has been achieved using
N-benzenesulfonyl-3,4-dibromopyrrole (3) as a common starting material. The key synthetic strategy
developed is the combined bromine-directed lithiation and palladium-catalyzed cross-coupling of 3 to
produce 3,4-diarylpyrrol-2-carboxylates. Regioselective iodination of the phenolic intermediate 24 was
thoroughly investigated for the synthesis of lukianol B..
17. Shotaro Hirao, Kenji Tara, Kazuyoshi Kuwano, Junji Tanaka, and Fumito Ishibashi, Algicidal Activity og Glycerolipids from Brown Alga Ishige sinicola toward Red Tide Microalgae, Bioscience, Biotechnology and Biochemistry, 76, 2, 372, 2012.02.
18. Shimizu, Tomoe, Hita, Katsuhiro, Paudel, Arjun, Tanaka, Junnji, Yamato, Takehiko, Synthesis of polymethyl substituted [2.2]metaparacyclophanes and their Lewis-acid induced isomerisation to [2.2]metacyclophanes, JOURNAL OF CHEMICAL RESEARCH-S , 10.3184/030823409X430185 , 2009, 4, 244-247 , 2009.04.
19. Fumiyasu Ono, Masayuki Hasegawa, Shuji Kanemasa, Junji Tanaka, Catalytic activation of nucleophile precursors with metal acetates in alcohol media and applications to enantioselective Michael addition reactions, Tetrahedron Letters, 49, 34, 5105-5107, 2008.08.
20. Fumiyasu Ono, Shuji Kanemasa, Junji Tanaka, Reusable nano-sized chiral bisoxazoline catalysts, Terahedron Lett, 10.1016/j.tetlet.2005.08.100, 46, 44, 7623-7626, 46, 7623-7626, 2005.10.
21. Kennosuke Itoh, Masayuki Hasegawa, Junji Tanaka, Shuji Kanemasa, Enatioselective Enol Lactone Synthesis under Double Catalytic conditions, Org. Lett, 10.1021/ol047872g, 7, 6, 979-981, 7, 979-981, 2005.03.
22. Shuji Kanemasa, Yoji Oderaotoshi, Shin-ichi Sakaguchi, Hidetoshi Yamamoto, Junji Tanaka, Eiji Wada, Dennis P. Curran, Transition-Metal Aqua Complexes of 4,6-Dibenzofuradily-2,2'-bis(4-phenyloxazoline). Effective Catalysis in Deals-Alder Reactions Showing Excellent Enantioselectivity, Extreme Chiral Amplification, and High Tolerance to Water, Alcoholes, Amines, and Acids, J. Am. Chem. Soc, 10.1021/ja973519c, 120, 13, 3074-3088, 120(13), 3074-3088 (1998), 1998.01.
23. Shuji Kanemasa, Yoji Oderaotoshi, Junji Tanaka, Eiji Wada, Temperature Dependent 1H NMR Study of the Substrate Complex Derived from Zinc(II) Perchlorate, (R,R)-4,6-Dibenzofurandiyl-2,2'-bis(4-phenyloxazoline), and 3-Acetyl-2-oxazolidinone. Evidence for Octahedral Structure of the Substrate Complex, Tetrahedron Letters, 10.1016/S0040-4039(98)01635-9, 39, 41, 7521-7524, 39(38) 7521-7524 (1998), 1998.01.
24. Junji Tanaka, Shuji Kanemasa, Ab Initio Study of Lewis Acid Catalyzed Nitrone Cycloaddition to Electron Deficient Alkenes. Does a Lewis Acid Catalyst Change the Reaction Mechanism?, Terahedron, 10.1016/S0040-4020(00)01045-0, 57, 5, 899-905, 57, 899-905 (2001), 2001.10.