Article
Chemistry, Multidisciplinary
Nikhil Srivastava, Hyun-Joon Ha
Summary: Aziridine displays different regioselective ring-opening reactions depending on the functional group of its alkyl substituents. This reaction can efficiently generate various substituted heterocycles.
FRONTIERS IN CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Jieun Choi, Taehwan Yu, Hyun-Joon Ha
Summary: The highly strained three-membered aziridine ring was activated as an aziridinium ion through alkylation of the ring nitrogen and subsequent ring opening with external nucleophiles. This method provides an easy route for synthesizing various N-alkylated amine-containing molecules with the introduction of external nucleophiles at either the alpha or beta position.
Article
Chemistry, Applied
Linlin Zhu, Qinyong Chen, Ying Wang, Huishan Huang, Wenyi Luo, Zhunxuan Li, Zhen Zhang, Nikos Hadjichristidis
Summary: A facile and effective method involving ring-opening copolymerization of N-sulfonyl aziridines towards cellulose has been developed for efficient oil/water separation. The modified cellulose paper material showed promising properties for efficient oil/water separations, with a grafting ratio ranging from 96 to 150% and a contact angle over 127°.
CARBOHYDRATE POLYMERS
(2021)
Article
Chemistry, Applied
Jan Doubsky, Stanislav Radl, Josef Cinibulk, Robert Klvana
Summary: An efficient and scalable synthesis method for fingolimod hydrochloride has been developed, using the aziridine regioselective ring-opening reaction as a key step. The method is industrially applicable and has been successfully applied to 500 g scales of the target product.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Polymer Science
Peng-Duo Song, Lei Xia, Xuan Nie, Guang Chen, Fei Wang, Ze Zhang, Chun-Yan Hong, Ye-Zi You
Summary: In this study, a ring-opening copolymerization method is reported to synthesize poly(thioester sulfonamide)s with highly alternative structures, high yields, and controlled molecular weights. This method combines the advantages of thioesters and amides, and can also be used to produce novel block copolymers.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Polymer Science
Taoguang Qu, Paul A. Rupar
Summary: A novel N-sulfonyl aziridine, N-((2-(trimethylsilyl)ethyl)sulfonyl)-2-methyl-aziridine (SES-MeAz), was synthesized and its controlled anionic ring-opening polymerization was studied. The desulfonylation of poly(SES-MeAz)s to form polypropylene imine (PPI) was achieved under mild conditions using tetrabutylammonium fluoride (TBAF). The first example of the selective removal of a sulfonyl protecting group from a poly(sulfonylazirdine) block copolymer and the first formation of a polysufonylaziridine-block-polypropylene imine copolymer were reported. Successful synthesis of three-armed star-shaped poly(SESMeAz)s with improved solubility compared to linear poly(SESMeAz)s was also demonstrated.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Polymer Science
Rui Chen, Ying Wang, Linlin Zhu, Zhen Zhang
Summary: An ultrafast method for controlled synthesis of polysulfonamides through organocatalytic anionic ring-opening polymerization (ROP) in the melt has been established. Using N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) as catalyst, poly(2-methyl-N-tosylaziridine) with molecular weight over 100 kg/mol can be synthesized in less than 90 s. Various initiators can be applied to achieve molecular weight and end-group controlled polymers under open-flask conditions.
JOURNAL OF POLYMER SCIENCE
(2021)
Article
Polymer Science
Chinh-Hoang Tran, Min-Woong Lee, Soo-Jeong Lee, Jin-Hyeok Choi, Eun-Gyeong Lee, Ha-Kyung Choi, Il Kim
Summary: A series of heterogeneous Zn-Co double metal cyanide (DMC) catalysts were investigated for ring-opening polymerization (ROP) of various cyclic monomers. It was found that inexpensive and commonly used organic solvents were effective complexing agents for the preparation of DMC catalysts, which showed high catalytic activity for the ROP of propylene oxide, epsilon-caprolactone, and delta-valerolactone. The chemical structures and compositions of the catalysts were determined using various techniques, and alpha, omega-hydroxyl-functionalized polyether and polyester polyols with high yields and tunable molecular weights were successfully synthesized in the presence of different initiators. Kinetic studies of the ROP of delta-valerolactone were also conducted to confirm the reaction mechanism.
Article
Chemistry, Organic
Santa Mondal, Shilpi Sarkar, Siddhartha S. Ghosh, Abu Taleb Khan
Summary: Regioselective ring-opening reactions were successfully used for the synthesis of beta-hydroxysulfides and beta-N-tosylaminosulfides, showing high selectivity, broad substrate compatibility, and mild reaction conditions. The newly synthesized compounds exhibited antiproliferative activity and anti-cancer properties.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jaehee Lee, Xuan Ju, Miseon Lee, Qi Jiang, Hwanjong Jang, Wan Shin Kim, Linglin Wu, Suja Williams, Xiao-Jun Wang, Xingzhong Zeng, Jenna Payne, Zhengxu S. Han
Summary: The copper-catalyzed regioselective and stereospecific coupling between aziridines and in situ generated pyridine Grignard reagents is reported in this study. This method enables the synthesis of beta-pyridylethylamines with diverse structures and functionalities, which are potential scaffolds for the synthesis of biologically active compounds commonly found in pharmaceuticals. Additionally, the synthesis of challenging chiral dihydroazaindoles was achieved through mild one-pot reaction conditions involving aziridine opening and nucleophilic cyclization.
Article
Chemistry, Multidisciplinary
Qilei Song, Hong Qiu, Lijun Liu, Guangzhao Zhang, Frederic Peruch, Stephane Carlotti, Junpeng Zhao
Summary: One-step sequence-selective block copolymerization requires strict catalytic control of monomer activity and enchainment order, especially for A(n)B(m)-type block copolymers from simple binary monomer mixtures. In this study, ethylene oxide (EO) and N-sulfonyl aziridine (Az) form a valid pair with a bicomponent metal-free catalyst. The optimal Lewis acid/base ratio allows the two monomers to block-copolymerize strictly in a reverse order (EO-first) compared to the conventional anionic route (Az-first). The livingness of the copolymerization enables the one-pot synthesis of multiblock copolymers by adding mixed monomers in batches. Calculation results suggest that the Janus effect of Lewis acid on the two monomers is crucial for enlarging the activity difference and reversing the enchainment order.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Hannah M. Holst, Jack T. Floreancig, Casey B. Ritts, Nicholas J. Race
Summary: This study demonstrates the synthesis of beta-phenethylamine products through the treatment of unsymmetrical 2,3-disubstituted aziridines with TiCl4, involving the intermediacy of a phenonium ion. Computational analysis provides insight into the reaction mechanism, especially the selectivity of phenonium opening.
Review
Chemistry, Organic
Du Qingfeng, Zhang Lu, Gao Feng, Wang Le, Zhang Wanbin
Summary: Epoxides and aziridines are important three-membered cyclic compounds and their asymmetric ring-opening reactions catalyzed by transition metals are efficient for constructing chiral molecules. This review focuses on the recent progress in this field, including the influence of catalysts, nucleophiles, and ligands, as well as discussing the possible reaction mechanisms, applications, and future development.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Polymer Science
Naofumi Naga, Tomoya Yamashita, Kasumi Toyama, Tamaki Nakano
Summary: In this study, PEI-based hard network polymers with controlled structure were successfully prepared by the ring-opening homo-polymerization of tri-aziridine compounds and dicarboxylic acids. The mechanical properties of the resulting polymers were influenced by reaction temperature and chain length of the dicarboxylic acid. The porous polymers obtained exhibited the ability to absorb various solvents, and the porosity could be controlled by the molecular structure of the dicarboxylic acid.
Article
Polymer Science
Wen Zhang, Dequan Chen, Xin Wang, Xingyi Xie
Summary: This study presents a simplified synthesis method for polyethylenimine (PEI) by using 2-haloethylamine in aqueous solution without separating the aziridine intermediate. The optimized two-stage process at different temperatures allows the conversion of 2-chloroethylamine into aziridine and PEI oligomer, and the subsequent ring-opening polymerization of aziridine to form PEI chains. The impurities in the final polymers are significantly reduced compared to traditional methods. This study provides insights into the mechanism of aziridine polymerization under basic conditions and offers a safer and more economical approach to manufacturing PEI polymers.
Article
Chemistry, Medicinal
Geoffrey Tucker, Binodh DeSilva, Jennifer Dressman, Michiho Ito, Takuya Kumamoto, Don Mager, Hanns-Christian Mahler, Anke H. Maitland-van der Zee, Giovanni M. Pauletti, Hitoshi Sasaki, Vinod Shah, Daniel Tang, Michael Ward
JOURNAL OF PHARMACEUTICAL SCIENCES
(2016)
Article
Chemistry, Organic
Kazuaki Katakawa, Mika Kainuma, Katsuya Suzuki, Saori Tanaka, Takuya Kumamoto
Article
Chemistry, Organic
Kanna Adachi, Sho Hasegawa, Kazuaki Katakawa, Takuya Kumamoto
TETRAHEDRON LETTERS
(2017)
Article
Biochemistry & Molecular Biology
Takuya Kumamoto, Marie Nakajima, Reina Uga, Naoko Ihayazaka, Haruna Kashihara, Kazuaki Katakawa, Tsutomu Ishikawa, Ryotaro Saiki, Kazuhiro Nishimura, Kazuei Igarashi
BIOORGANIC & MEDICINAL CHEMISTRY
(2018)
Article
Chemistry, Organic
Mika Kainuma, Ai Yamada, Kazuaki Katakawa, Takuya Kumamoto
Review
Chemistry, Organic
Kazuaki Katakawa, Takuya Kumamoto
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2018)
Article
Biochemistry & Molecular Biology
Makoto Hashimoto, Takaaki Taguchi, Kazuki Ishikawa, Ryuichiro Mori, Akari Hotta, Susumu Watari, Kazuaki Katakawa, Takuya Kumamoto, Susumu Okamoto, Koji Ichinose
Article
Pharmacology & Pharmacy
Hiroshi Arakawa, Hiroyuki Yamada, Kazutaka Arai, Takumi Kawanishi, Nobuhiro Nitta, Sayaka Shibata, Eiko Matsumoto, Kentaro Yano, Yukio Kato, Takuya Kumamoto, Ichio Aoki, Takuo Ogihara
INTERNATIONAL JOURNAL OF PHARMACEUTICS
(2020)
Article
Chemistry, Applied
Hideyoshi Tsuchiya, Minoru Iwamoto, Hidetoshi Miyamoto, Chihiro Sakumoto, Tokihiko Tamamizu, Yasuo Inoshita, Yuzo Koyama, Yoshinori Sato, Takuya Kumamoto
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2020)
Article
Chemistry, Medicinal
Yumi Shintani, Koichi Kato, Masashi Kawami, Mikihisa Takano, Takuya Kumamoto
Summary: This study explored methods for direct N-1-selective methylation of phenytoin using potassium bases in THF, yielding N-1-monomethylated phenytoin and found applicability for various hydantoins and alkyl halides. Despite examining the effects of methylated phenytoins on P-glycoprotein, none showed inhibitory activity toward rhodamine 123 efflux by P-glycoprotein.
CHEMICAL & PHARMACEUTICAL BULLETIN
(2021)
Article
Biochemistry & Molecular Biology
Takuya Kumamoto, Mika Kainuma, Azusa Takahashi, Yoshika Matsuo, Kazuaki Katakawa, Takaaki Taguchi, Koji Ichinose
Summary: This article reports the total synthesis of 6-deoxydihydrokalafungin (DDHK) and its epimer, epi-DDHK, as well as a semisynthetic approach from (S)-DNPA. Different reaction sequences were used to successfully obtain these two compounds.
Article
Chemistry, Organic
Hiroki Miyake, Ryo Nakajima, Takuya Kumamoto
Summary: The asymmetric total synthesis of angucycline antibiotics (S)-brasiliquinones B and C was achieved by constructing the benz[a]anthraquinone core through oxidative cyclization. The synthetic products confirmed the (S)-configuration of natural brasiliquinones.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Makoto Hashimoto, Susumu Watari, Takaaki Taguchi, Kazuki Ishikawa, Takuya Kumamoto, Susumu Okamoto, Koji Ichinose
Summary: In this study, we identified two enzymes, ActVA-ORF4 and ActVA-ORF3, involved in the last step of ACT biosynthesis. ActVA-ORF4 catalyzes the intermolecular C-C bond formation using DHK-OH as the substrate, while ActVA-ORF3 is a quinone-forming enzyme that produces the coupling substrate DHK-OH and the final product ACT.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Takuya Kumamoto, Sho Hasegawa, Kanna Adachi, Kazuaki Katakawa
Summary: The total synthesis of (+/-)-4-deoxyblennolide C was achieved by constructing a quaternary carbon, oxidative cleavage of alkene moiety, and the formation of xanthone framework. This work provides a method to prepare deoxy analogues of xanthone antibiotics.
Review
Chemistry, Organic
Takuya Kumamoto, Kazuaki Katakawa
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
