Department of Chemistry, Nara University of Education
Takabatake-cho, Nara 630-8528, Japan

(Last updated 2022/4/1) 




有機合成化学は、有機分子を作り出すあらゆる先端技術の基幹研究分野として重要であり、また、21世紀のニーズに応えていく必要がある。本研究室では、効率的・選択的新規有機反応の開発、再生可能な物質を利用する新規合成反応の開発、その新反応を用いた生理活性分子の創製、新しいマテリアルの創製などの研究を進めている。研究テーマとして、高い反応性を持つ基質の合成反応への利用、触媒を用いたまたは無触媒による新規効率的反応の設計、その不斉合成への応用 、新反応を利用した有用物質の合成などの研究を行なっている。


We are interested in the development of new efficient reactions and synthetic methods, including use of renewable resources and their application to biologically active compounds and new organic materials. In our research to date, we have shown that ethenetricarboxylate derivatives are highly electrophilic Michael acceptors or electron-deficient C=C components in various synthetic reactions. Lewis acids also promote the reactions of ethenetricarboxylate derivatives efficiently. Novel cyclization and addition reactions gave the compounds shown below.

For example, intramolecular [2+2] and [4+2] cycloaddition reactions of cinnamylamides of ethenetricarboxylate in sequential processes have been studied. Reaction of 1,1,2-ethenetricarboxylic acid 1,1-diethyl ester and trans-cinnamylamines in the presence of EDCI/HOBt/Et3N led to pyrrolidine products in one pot, via intramolecular [2+2], [4+2] and some other cyclizations. The types of the products depend on the substituents on benzene ring and the reaction conditions (1).

Inter- and intramolecular cycloaddition reactions of ethenetricarboxylates with styrene and α-halostyrene moieties under the Lewis acid-promoted or sequential thermal conditions have been investigated. The stereoselective cyclobutane formations for intermolecular reactions have been found (2). The intramolecular cycloaddition reactions of a series of styrene-functionalized ethenetricaroxylate amides, including in situ generated derivatives, showed high diversity of reaction modes depending on the structures and substituents of the substrates (3).

Furthermore, sequential Knoevenagel condensation/cyclization leading to indene and benzofulvene derivatives have been developed. The reaction of 2-(1-phenylvinyl)benzaldehyde with malonates gave benzylidene malonates, cyclized indenes, and dehydrogenated benzofulvenes. The product selectivity depends on the reaction conditions (4).



Current Group Members:

Ryo Onari: Yuta Mori: Yuki Iwataki: Kosuke Kitano: Tomoya Niegawa: Ryota Torii: Zhichao Wang (Osaka Pref. Univ.)

Representative Recent References:


Sequential Knoevenagel Condensation/Cyclization for the Synthesis of Indene and Benzofulvene Derivatives. Yamazaki, S.; Katayama, K.; Wang, Z.; Mikata, Y.; Morimoto, T.; Ogawa, A. ACS Omega 2021, 6, 28441-28454.


Thiepanes and Thiepines, Yamazaki, S. Comprehensive Heterocyclic Chemistry IV, 2021 Elsevier Inc.


Three or Four Heteroatoms Including at Least One Selenium or Tellurium, Yamazaki. S. Comprehensive Heterocyclic Chemistry IV, 2021 Elsevier Inc.


Inter- and Intramolecular Cycloaddition Reactions of Ethenetricarboxylates with Styrenes and Halostyrenes, Yamazaki, S.; Wang, Z.; Iwata, K.; Katayama, K.; Sugiura, H.; Mikata, Y.; Morimoto, T.; Ogawa, A. Synthesis 2021, 53, 731-753.


1,3-Dioxins, Oxathiins, Dithiins, and Their Benzo Derivatives, Yamazaki, S. Comprehensive Heterocyclic Chemistry IV, 2020 Elsevier Inc.


Sequential Intramolecular Diels–Alder Reaction of 3-Heteroaryl-2-propenylamides of Ethenetricarboxylate, Sugiura, H.; Yamazaki, S.; Ogawa, A. J. Heterocyclic Chem. 2019, 56, 2592-2603.


Intramolecular Cyclization of 3,3-Diarylpropenylamides of Electron-deficient Alkenes: Stereoselective Synthesis of Functionalized Hexahydrobenzo[f]isoindoles, Sugiura, H.; Yamazaki, S.;  Go, K.;  Ogawa, A. Eur. J. Org. Chem. 2019, 204-220.


Synthesis of piperidines via intramolecular hydride transfer from α-amino sp3 carbon atoms to ethenetricarboxylate-derived fragments and further cyclization, Yamazaki, S.; Naito, T.; Tatsumi, T. Kakiuchi, K. ChemistrySelect 2018, 3, 4505–4511.


Lewis Acid Catalyzed Cyclization Reactions of Ethenetricarboxylates via Intramolecular Hydride Transfer, Yamazaki, S.; Naito, T.; Niina, M.; Kakiuchi, K. J. Org. Chem. 2017, 82, 6748−6763.


Intramolecular [2+2] and [4+2] Cycloaddition Reactions of Cinnamylamides of Ethenetricarboxylate in Sequential Processes, Yamazaki, S.; Sugiura, H.; Ohashi, S.; Ishizuka, K.; Saimu, R.; Mikata, Y.; Ogawa, A. J. Org. Chem. 2016, 81, 10863-10886.



Nara University of Education