Article
Chemistry, Organic
Shogo Nakamura, Soshi Nishino, Koji Hirano
Summary: A copper-catalyzed regioselective hydroamination method was developed to synthesize alpha-aminophosphonates from alpha,beta-unsaturated phosphonates, which are of interest in medicinal chemistry. The use of an umpolung, electrophilic amination strategy with a hydroxylamine derivative is key to achieving the desired regioselectivity, as compared to the conventional nucleophilic hydroamination conditions with the parent amine. The article also discusses the asymmetric synthesis using a chiral bisphosphine ligand and its application in a related silylamination reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Nityananda Ballav, Suman Dana, Mahiuddin Baidya
Summary: The hydrocarbofunctionalization of allyl amines connected to the picolinamide directing group is developed under Pd(II) catalysis. The strategy is based on a nucleopalladation concept and can effectively produce indole derivatives. The synthetic utilities of this reaction, including the Pictet-Spengler cyclization and beta-carboline synthesis, were demonstrated. Mechanistic studies indicate that the reaction proceeds through an irreversible nucleopalladation pathway.
Article
Chemistry, Organic
Nityananda Ballav, Suman Dana, Mahiuddin Baidya
Summary: This study introduces a Pd(II)-catalyzed hydrocarbofunctionalization method for allyl amines connected to the picolinamide directing group. The approach is based on the concept of nucleopalladation and a wide range of indoles effectively participate to produce valuable tryptamine derivatives with high yields. Synthetic utilities are showcased through substrate diversification bearing bioactive core, Pictet-Spengler cyclization, and beta-carboline synthesis. A mechanistic study suggests an irreversible nucleopalladation step, while protodepalladation follows a reversible pathway.
Article
Chemistry, Organic
Liqiang Yin, Murong Xu, Ye Wang, Huihui Xie, Yang Yuan, Chengyu Wang, Yuan-Ye Jiang, Yanzhong Li
Summary: A Co(II)-catalyzed cycloaddition reaction of alkynyl ketones and 2-acetylpyridines has been developed, with regioselective insertion of the alkynone. This reaction results in the formation of polysubstituted benzene derivatives in good to excellent yields, showing the potential for novel synthesis methods in organic chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Chen-Fei Liu, Zi-Chao Wang, Xiaohua Luo, Jiawei Lu, Charyl Hui Min Ko, Shi-Liang Shi, Ming Joo Koh
Summary: Asymmetric transition-metal catalysis has a significant impact on chemical synthesis, but non-precious metal-catalysed strategies for enantioenriched compounds with multiple stereogenic centers are rare. This study presents a sterically encumbered chiral N-heterocyclic carbene-Ni(O) catalyst, combined with an organotriflate and a metal alkoxide as hydride donor, to promote 1,2-hydroarylation and hydroalkenylation reactions of various alkenes and 1,3-dienes.
Article
Chemistry, Organic
Rahul K. Shukla, Atul K. Chaturvedi, Subir Pal, Chandra M. R. Volla
Summary: In this study, a Pd(II)-catalyzed regioselective hydrocarbofunctionalization of unactivated alkenes was demonstrated. The regioselectivity of the reaction was controlled by using a bidentate auxiliary and specific alkynes, leading to the formation of 1,6-dicarbonyl compounds through a cascade sequence.
Article
Chemistry, Organic
Mercedes Zurro, Sergio Torres-Oya, Estibaliz Merino
Summary: This study describes a one-step synthesis of the anticancer drug bicalutamide from N-arylacrylamide using visible light. The approach involves a photocatalytic redox process, specifically a one-pot hydroxysulfonylation reaction. By using Na2Eosin Y as a photocatalyst and blue light, a variety of α-hydroxysulfonylamides with a quaternary center can be obtained with complete regioselectivity via a radical process, achieving moderate to good yields.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Xabier del Corte, Adrian Lopez-Frances, Edorta Martinez de Marigorta, Francisco Palacios, Javier Vicario
Summary: This study reports a formal [3+3] cycloaddition reaction of cyclic enamines and alpha,beta-unsaturated ketones catalyzed by ytterbium, showing high stereoselectivity and regioselectivity. The resulting bicyclic 1,4-dihydropyridines were evaluated as antiproliferative agents against A549 and SKOV3 human tumor cell lines, exhibiting good toxicities with high selectivity towards non-malignant cell lines MRC5.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Jinfeng Huang, Yimin Jia, Xiangyu Li, Jianli Duan, Zhong-Xing Jiang, Zhigang Yang
Summary: A highly regioselective copper-catalyzed reaction has been developed for the first time to access tetrasubstituted allene derivatives containing halogen and CF3 groups with good to excellent yields. This practical and convenient method is compatible with a wide range of functional groups and has shown promising applications in the gram-scale preparation and late-stage functionalization of biologically active molecules.
Article
Chemistry, Organic
Yongxing Zhao, Rui Li, Qingzheng Zhao, Jinzhong Yao, Maozhong Miao
Summary: Unprecedented dimerizations of 2H-azirines have been achieved through the catalysis of palladium and silver. By altering the reaction conditions, fully aryl-substituted pyrrole and pyrimidine derivatives were obtained with moderate yields and regiospecificity. Control experiments demonstrated distinct catalytic effects of the two transition metals, and the proposed catalytic cycles provided plausible explanations for the chemodivergence and regioselectivity.
Article
Chemistry, Multidisciplinary
Dong-Tai Xie, Hong-Lei Chen, Dian Wei, Bang-Yi Wei, Zheng-Hu Li, Jian-Wu Zhang, Wei Yu, Bing Han
Summary: A novel distal radical rearrangement of alkoxyphosphine is developed for the first time and applied to the regioselective radical fluoroalkylphosphorylation of unactivated olefins. By employing a one-pot two-step reaction under CFL (compact fluorescence light) irradiation, a series of fluoroalkylphosphorylated alkyl iodides and alcohols are easily synthesized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Aleksandra Nilova, Paul A. Sibbald, Edward J. Valente, Gisela A. Gonzalez-Montiel, H. Camille Richardson, Kevin S. Brown, Paul Ha-Yeon Cheong, David R. Stuart
Summary: This study describes a method for synthesizing 1,2,3,4-tetrasubstituted benzenoid rings, addressing previous challenges in regioselective synthesis of these compounds. By using substituted arynes derived from aryl(Mes)iodonium salts, a range of densely functionalized 1,2,3,4-tetrasubstituted benzenoid rings can be accessed. The study demonstrates improved conditions for generating arynes at room temperature and in shorter reaction times, allowing for post-synthetic elaboration via palladium-catalyzed coupling.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Kentaro Iwaki, Kazuhiro Tanagawa, Soichiro Mori, Koki Maruno, Yuji Sumii, Osamu Nagata, Norio Shibata
Summary: In this study, we reported a metal-free hydration reaction of pyridine-SF4-alkynes under acidic conditions, which synthesized pyridine-SF4-methyl ketones with yields ranging from 59% to 93%. We further demonstrated the synthetic applications of these compounds, including chlorination, NaBH4 reduction, Baeyer-Villiger oxidation, and the generation of enol triflates. These compounds show promise as useful building blocks in the synthesis of a wide range of SF4-containing drug candidates.
Article
Chemistry, Physical
Camilla Pfeffer, Nick Wannenmacher, Wolfgang Frey, Rene Peters
Summary: Enynes are important motifs in bioactive compounds and can be synthesized through various mechanisms and reaction conditions. Bimetallic catalysts can achieve the synthesis of (E)-configured enynes, leading to different reaction products. Mechanistic studies have identified the significance of acetylide Pd bridging in influencing the reaction outcomes.
Article
Chemistry, Multidisciplinary
Hirokazu Moniwa, Ryo Shintani
Summary: A new and complementary method using copper-catalyzed regio- and anti-selective addition of silylboronates to unsymmetric internal alkynes has been developed for the synthesis of structurally defined tetrasubstituted alkenes. Various unactivated alkynes can be employed with high selectivity under simple and mild conditions, allowing further functionalization of the alkene products utilizing silyl and boryl groups.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biology
Iulian Ilies, Rifat Sipahi, Gunther K. H. Zupanc
JOURNAL OF THEORETICAL BIOLOGY
(2018)
Article
Chemistry, Multidisciplinary
Hayato Tsuji, Anna Ichimura, Mizuki Kudo, Junpei Sukegawa, Eiichi Nakamura
CHEMISTRY-AN ASIAN JOURNAL
(2019)
Review
Chemistry, Multidisciplinary
Hayato Tsuji, Eiichi Nakamura
ACCOUNTS OF CHEMICAL RESEARCH
(2019)
Article
Chemistry, Multidisciplinary
Kohei Iwai, Hiroshi Yamagishi, Colin Herzberger, Yuji Sato, Hayato Tsuji, Ken Albrecht, Kimihisa Yamamoto, Fumio Sasaki, Hiroyasu Sato, Aswin Asaithambi, Axel Lorke, Yohei Yamamoto
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Victor Bonal, Marta Morales-Vidal, Pedro G. Boj, Jose M. Villalvilla, Jose A. Quintana, Naiti Lin, Shoya Watanabe, Hayato Tsuji, Eiichi Nakamura, Maria A. Diaz-Garcia
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2020)
Article
Chemistry, Multidisciplinary
Samara Medina Rivero, Rui Shang, Hiroyoshi Hamada, Qifan Yan, Hayato Tsuji, Eiichi Nakamura, Juan Casado
Summary: The study focused on electron acceptor and donor spiro-conjugated dimers based on specific compounds, investigating the existence of SOMO-HOMO energy level inversion through the radical forms of charged species. The results showed non-Aufbau energy properties in certain radical ions, attributed to spiro-conjugation and electron-electron repulsion effects.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Review
Chemistry, Multidisciplinary
Hayato Tsuji
Summary: Carbon-bridged oligo(phenylenevinylene)s (COPVs) have a rigid planar molecular structure, excellent functionality and high stability, and exhibit phenomena at room temperature that conventional molecules only show at cryogenic temperatures.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Organic
Keisuke Iwata, Yasunobu Egawa, Katsunori Yamanishi, Hayato Tsuji
Summary: The acid-induced intramolecular cyclization of 1,1-disubstituted 3-aryl-2,3-dibromoallylalcohols leads to the formation of 2,3-dibromo-1H-indene derivatives and tetrabromodihydro-s-indacenes. These multi-brominated compounds can serve as versatile building blocks for the synthesis of various indene and indacene derivatives. The synthesis of dialkylmethylene-bridged oligo(phenylenevinylene)s demonstrates the attractive photophysical properties of these compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Hayato Tsuji, Masaki Nakahata, Mafumi Hishida, Hideki Seto, Ryuhei Motokawa, Takeru Inoue, Yasunobu Egawa
Summary: This study investigates the aggregation behavior of hydrophobic solutes in water-THF solution and the role of THF. A model is proposed based on experimental results, suggesting that hydrophobic solutes are molecularly dispersed in the low-water-content region and form mesoscopic particles upon increasing the water fraction.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Materials Science, Multidisciplinary
Hayato Tsuji, Akihiro Shitomi, Naoto Hamaguchi, Yasunobu Egawa, Victor Bonal, Pedro G. Boj, Jose M. Villalvilla, Jose A. Quintana, Maria A. Diaz-Garcia
Summary: A naphtho[2,1-b:6,5-b ']difuran derivative has been identified as an effective violet-emitting laser dye, showing amplified spontaneous emission at 413 nm in polystyrene film. Lasing was also demonstrated using all-polymeric distributed-feedback lasers emitting at 411-417 nm.
JOURNAL OF MATERIALS CHEMISTRY C
(2021)
Article
Chemistry, Multidisciplinary
Takeru Inoue, Makoto Tsurui, Hiroshi Yamagishi, Yuma Nakazawa, Naoto Hamaguchi, Shoya Watanabe, Yuichi Kitagawa, Yasuchika Hasegawa, Yohei Yamamoto, Hayato Tsuji
Summary: In this study, donor-acceptor-donor conjugates were synthesized and found to serve as efficient and stable long-wavelength photoluminescent dyes in organic and aqueous media. Specifically, Cz-COPV2-BBTz-COPV2-Cz showed high photoluminescence quantum yield in the near-infrared region.
Article
Materials Science, Multidisciplinary
Victor Bonal, Jose M. Villalvilla, Jose A. Quintana, Pedro G. Boj, Naiti Lin, Shoya Watanabe, Karolis Kazlauskas, Ona Adomeniene, Saulius Jursenas, Hayato Tsuji, Eiichi Nakamura, Maria A. Diaz-Garcia
ADVANCED OPTICAL MATERIALS
(2020)
Article
Chemistry, Physical
Takahiro Doba, Tatsuaki Matsubara, Laurean Ilies, Rui Shang, Eiichi Nakamura
Review
Chemistry, Organic
Hayato Tsuji, Eiichi Nakamura
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2020)
Article
Chemistry, Physical
Shoya Watanabe, Katsunori Yamanishi, Hayato Tsuji