KEIO RESEARCHERS INFORMATION SYSTEM

Papers 【 Display / hide 】

Papers 【 Display / hide 】

• Oxa-TriQuinoline: A New Entry to Aza-Oxa-Crown Architectures

  Kobayashi T., Kumagai N.

  Angewandte Chemie - International Edition 62 ( 32 )  2023.08

  Research paper (scientific journal), Joint Work, Lead author, Accepted,  ISSN  14337851

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  A new 15-membered-macrocyclic molecular entity, oxa-TriQuinoline (o-TQ), was designed and synthesized. In o-TQ, three oxygen atoms were joined onto three quinoline units at the 2- and 8-positions in a head-to-tail fashion by three-fold SNAr reactions, giving rise to the characteristic N3O3 aza-oxa-crown architecture. o-TQ can serve as a new tridentate nitrogen ligand to capture a CuI cation and adopt a bowl shape, before supramolecular complexation with corannulene and [12]cycloparaphenylene (CPP) occurs through π–π and CH–π interactions. In the presence of the CuI cation, the non-emissive o-TQ becomes a highly emissive material in the solid state, whereby the emission wavelengths depend on the ancillary ligand on the CuI cation. The o-TQ/CuI complex is able to promote carbene catalysis to provide a range of enamines with a gem-difluorinated terminus.

  • Access to Document (DOI)

• iso-TEtraQuinoline (i-TEQ): an inherently chiral N4 macrocyclic quinoline tetramer

  Yagami R., Xu W., Kobayashi T., Nagata Y., Kumagai N.

  Chemical Science 16 ( 24 ) 10714 - 10721 2025.05

  Research paper (scientific journal), Joint Work, Accepted,  ISSN  20416520

  　View Summary

  Chiral macrocycles are attracting growing interest due to their broad applicability as ligands in asymmetric catalysis and as host molecules for chiral recognition. Robustness and high thermodynamic stability can be effectively achieved by strategically linking aromatic panels to construct an axially chiral macrocyclic framework. Cyclic concatenation of four quinoline units affords a fully sp²-hybridized, non-planar macrocycle featuring four inwardly oriented, coordinatively active pyridyl nitrogen atoms. The previously reported tetramer TEtraQuinoline (TEQ) exhibits head-to-tail connectivity of its quinoline units, affording an achiral architecture possessing S<inf>4</inf> symmetry. Herein, we report the design and synthesis of iso-TEtraQuinoline (i-TEQ), an inherently chiral analogue featuring head-to-head connectivity at the 2,2′- and 8,8′-positions, which gives rise to a D<inf>2</inf>-symmetric architecture. Detailed comparative investigations of the connectivity isomers i-TEQ and TEQ revealed an array of distinct characteristics, including the overall architecture, intrinsic macrocyclic strain, spatial orientation of nitrogen lone pairs, thermodynamic stability, racemisation behaviour, metal complex stability, and circularly polarised luminescence.

  • Access to Document (DOI)

• Insights into Coordination and (Semi-)Rigidity in the Molecular Design of Bicyclic Heterocycle Frameworks

  Kobayashi T.; Takuya S.; Naoya K.

  Chemistry Letters  2026

  Research paper (scientific journal), Joint Work, Lead author, Accepted

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  Macrocyclic compounds, exhibiting unique properties arising from their large-ring frameworks, have captivated the attention of organic chemists over the last few decades. These molecules serve specific functions across disciplines, including synthetic chemistry, materials science, and biology. Representative molecules in this category, including crown ethers, calix[n]arenes, and porphyrinoids composed of ether/phenol/pyrrole subunits, exhibit unparalleled structural and functional diversity. In contrast, macrocycles exploiting quinoline/quinazoline as key building blocks to construct specific macrocyclic architectures have received limited attention and are much less explored. In this Highlight Review, we summarize our recent advances in oligo-quinoline/quinazoline macrocycles. Emphasis is focused on synthetic strategies, structural features, and emerging applications in organometallic, supramolecular, and photophysical chemistry. We anticipate that these collective results will guide new molecular designs within the broader family of heterocycle-based macrocycles.

  • Access to Document (DOI)

• Enlarged-TriQuinoline (Enl-TQ): Disparity in Chemical Behaviors by Geometric Scaling of the Trimeric Quinoline Ring System

  Yamashita M., Tsutsumi R., Kobayashi T., Kumagai N.

  Chemistry an Asian Journal 20 ( 17 )  2025

  Research paper (scientific journal), Joint Work, Accepted,  ISSN  18614728

  　View Summary

  TriQuinoline (TQ), a quasi-planar cyclic quinoline trimer concatenated at the 2,8-positions in a head-to-tail arrangement, strongly captures a proton at the 12-membered inner cycle and exhibits unusual physicochemical properties, including unexpected water solubility and the ability to engage in complexation with other π-conjugated molecules. In this study, we designed and synthesized its expanded analog, coined Enlarged-TriQuinoline (Enl-TQ), in which three alkyne units are embedded between three quinoline units to acquire an expanded planar 18-membered ring system. DFT calculations and X-ray crystallographic analysis revealed its planar architecture with three inwardly facing pyridinic nitrogen atoms. Despite its structural similarity to TQ, Enl-TQ displayed distinct host capability and photophysical characteristics.

  • Access to Document (DOI)

• Development of Unique Quinoline-Based Macrocyclic Systems and Strategic Applications in Versatile Chemistry

  Kobayashi T., Xu W., Kumagai N.

  Journal of Synthetic Organic Chemistry 83 ( 5 ) 386 - 394 2025

  Research paper (scientific journal), Joint Work, Lead author, Accepted,  ISSN  00379980

  　View Summary

  Macrocyclic compounds exhibit unique properties due to their large ring─shaped structures, which have captivated chemists in recent decades. These molecules exert specific functions in a multidisciplinary basis, e.g. chemistry, materials science, and biology. Crown ethers, calix [n] arenes, and porphyrinoids, which contain several ether／phenol／pyrrole subunits, represent milestones in these molecular categories with unparalleled functional diversity. In contrast, macrocycles exploiting quinoline as a key unitary element to construct specific macrocyclic architecture have received limited attention and been barely explored. In this report, we summarize the recent advances in oligo─ quinoline macrocycles TriQuinoline (TQ), oxa─TriQuinoline (o─TQ), TEtraQuinoline (TEQ), and indole／quinoline hybrid macrocycle In2Q2. Particular emphasis is placed on the synthesis, structure, and application of these molecules in organometallic and supramolecular chemistry, which may guide new molecular designs in the heterocycle─based macrocycle family.

  • Access to Document (DOI)

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Presentations 【 Display / hide 】

Presentations 【 Display / hide 】

• 酸素原子ドープドキノリンオリゴマー群の合成と多座配位子としての機能開拓

  小林透威

  [Domestic presentation]  ２０２５年度関東支部若手研究者のためのセミナー (東京) , 

  2025.08

  , 

  Oral presentation (invited, special)

• トリポーダル型oxa-TriQuinoline (o-TQ) 配位子によるCuカルベン挿入反応の高活性化

  小林透威，熊谷直哉

  [Domestic presentation]  日本薬学会 第146年会 (大阪) , 

  2026.03

  , 

  Poster presentation

• キノリン環を組み込んだ窒素ドープ型カーボンナノリングの合成

  山下舞，小林透威，熊谷直哉

  [Domestic presentation]  日本薬学会 第146年会 (大阪) , 

  2026.03

  , 

  Oral presentation (general)

• キノリン環を組み込んだ窒素ドープ型カーボンナノリングの合成

  山下舞，小林透威，熊谷直哉

  [Domestic presentation]  日本化学会 第106春季年会（2026） (千葉) , 

  2026.03

  , 

  Oral presentation (general)

• 窒素原子架橋型キノリン3量体aza-TriQuinoline（a-TQ）の合成

  中森佳亮，根本春美，小林透威，熊谷直哉

  [Domestic presentation]  日本化学会 第106春季年会（2026） (千葉) , 

  2026.03

  , 

  Poster presentation

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Awards 【 Display / hide 】

Awards 【 Display / hide 】

• 優秀発表賞

  2023.05, 第21回次世代を担う有機化学シンポジウム

  Type of Award： Award from Japanese society, conference, symposium, etc.

• ポスター賞

  2023.09, 第33回基礎有機化学討論会

  Type of Award： Award from Japanese society, conference, symposium, etc.

• 優秀発表賞

  2023.03, 日本薬学会 第143年会

  Type of Award： Award from Japanese society, conference, symposium, etc.

• 優秀口頭発表賞

  2020.09, 日本薬学会 第64回関東支部大会

  Type of Award： Award from Japanese society, conference, symposium, etc.

Courses Taught 【 Display / hide 】

Courses Taught 【 Display / hide 】

• CHEMISTRY OF BIOACTIVE SUBSTANCES

  2026

• BACHELOR'S THESIS

  2026

• EARLY EXPOSURE TO INDUSTRY

  2026

• STUDY OF MAJOR FIELD (MOLECULAR DESIGN)

  2026

• RESEARCH FOR BACHELOR'S THESIS 1

  2026

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Memberships in Academic Societies 【 Display / hide 】

Memberships in Academic Societies 【 Display / hide 】

• 有機合成化学協会, 

  2024

  -

  Present

• 日本化学会, 

  2021

  -

  Present

• 日本薬学会, 

  2019

  -

  Present