Article
Chemistry, Physical
Zhi Zhou, Gerard Roelfes
Summary: The article describes a tandem Michael addition/enantioselective protonation reaction catalyzed by an artificial enzyme in water. Through the use of abiological catalytic sites and a Lewis acid Cu(II) complex, high stereocontrol was achieved. This illustrates the potential of exploiting synergistic catalysis in artificial enzymes for challenging reactions.
Article
Chemistry, Multidisciplinary
Francesco Vaghi, Giorgio Facchetti, Isabella Rimoldi, Matteo Bottiglieri, Alessandro Contini, Maria Luisa Gelmi, Raffaella Bucci
Summary: Multiple studies have shown that the pyrrolidine nucleus is more efficient as organocatalysts for the condensation of aldehydes with electrophiles via enamine, compared to piperidine or morpholine. The low reactivity of morpholine-enamines is due to the presence of oxygen on the ring and the pyramidalisation of nitrogen, which decreases the nucleophilicity of the enamine. Therefore, finding efficient morpholine organocatalysts is a challenging task.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Physical
Jian-Hua Liu, Qing Zhou, Yao Lin, Zhu-Lian Wu, Tian Cai, Wei Wen, Yan-Min Huang, Qi-Xiang Guo
Summary: In this study, a highly efficient atom-economic asymmetric alpha-allylation method using chiral-aldehyde/palladium catalyst was reported. This method enables the asymmetric alpha-allylation of different 1,3-dienes and allenes with N-unprotected amino acid esters, leading to the synthesis of alpha,alpha-disubstituted chiral alpha-amino acid esters with high efficiency, good yields, and stereoselectivities. No N-allylation byproducts were observed in these reactions. Two reaction models were proposed based on mechanistic control experiments. Overall, this work demonstrates a new approach for preparing structurally diverse chiral amino acids and provides insights for developing chiral-aldehyde catalytic systems.
Article
Chemistry, Multidisciplinary
Minghui Zhu, Qinglong Zhang, Weiwei Zi
Summary: The study presents a dual-metal catalyzed diastereodivergent coupling method for the synthesis of beta-amino alcohols with multiple stereoisomers, enabling the concise preparation of natural products such as mycestericins F and G.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Dominik Albat, Martin Reiher, Joerg-Martin Neudoerfl, Hans-Guenther Schmalz
Summary: A new class of chiral C-2-symmetric diphosphines (MediPhos) has been shown to be highly effective in the Pd-catalyzed asymmetric N-allylation of amino acid esters. A new and improved method for preparing these ligands through bidirectional S(N)2-coupling has been described, providing access to nine ligands with branched alkyl substituents, which exhibited excellent performance in enantioselective Pd-catalyzed N-allylation reactions. Additionally, the synthesized allylic amines were utilized in the stereoselective synthesis of conformationally restricted dipeptide analogs.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Daniel Sowa Prendes, Florian Papp, Nagesh Sankaran, Nardana Sivendran, Frederike Beyer, Christian Merten, Lukas J. Goossen
Summary: Arylglycines, which are important pharmacophores in several top-selling drugs, can now be synthesized from abundant aryl chlorides using a Pd-catalyzed Schollkopf-type amino acid synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Feng Jiang, Tengfei Meng, Ying Zhou, Zhenying Xiong, Yupei Zhao, Wengang Guo
Summary: We report an enantio- and diastereodivergent synthesis of enantioenriched fluorenes with broad substrate scope and high enantioselectivity (up to 99% ee) under low catalyst loading (0.1 mol %). The success of this method lies in the pseudo-diastereodivergent desymmetrization of stereoisomers of meso-epoxides enabled by the same organocatalyst. Furthermore, some of the chiral fluorenes obtained exhibit high fluorescence quantum yields (up to 76.6%), as evidenced by photophysical properties studies.
Article
Chemistry, Multidisciplinary
Bastian Jakob, Andreas M. Diehl, Kathrin Horst, Harald Kelm, Georg Manolikakes
Summary: Here we report a palladium-catalyzed asymmetric three-component synthesis of α-arylglycine derivatives. This operationally simple method utilizes glyoxylic acid, sulfonamides, and arylboronic acids as starting materials to obtain α-arylglycine scaffold in good yields and enantioselectivities. The synthesized products can be directly used as building blocks in peptide synthesis.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hu Tian, Hong-Ming Zhang, Liang Yin
Summary: In this article, a copper(I)-catalyzed asymmetric conjugate addition/protonation with selenols and alpha-substituted alpha,beta-unsaturated thioamides is described, which produces a series of chiral selenides with high to excellent enantioselectivity. The reaction shows a broad substrate scope for both selenols and alpha-substituted alpha,beta-unsaturated thioamides. The catalytic system is also successfully used for asymmetric selenation of beta-substituted alpha,beta-unsaturated thioamides. A [Cu-(R,R-P)-TANIAPHOS]-SePh species is identified by Se-77 NMR spectra, with a chemical shift at delta 462 ppm. Furthermore, a {[Cu-(R)-TOL-BINAP]-SePh}(2) species is characterized by X-ray analysis, confirming the formation of Cu-Se bond in the reaction. Finally, the straightforward transformations of the thioamide group to amine and thioester are demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yu-Chao Wang, Zhao-Xin Xiao, Miao Wang, Shao-Qian Yang, Jin-Biao Liu, Zhi-Tao He
Summary: This study presents modular protocols for 1,5-conjugate addition reactions via palladium hydride catalysis, which has been considered unfeasible. The results show that the 1,5-conjugate addition products can be conveniently transformed into various privileged enantioenriched motifs, indicating the potential applications of this method in synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Irma Garcia-Monzon, Jorge Borges-Gonzalez, Tomas Martin
Summary: The heterogenization of homogeneous catalysts onto a solid support is a crucial step towards sustainable chemistry. In this study, we developed a series of polymer-supported tetrahydropyran-based hybrid dipeptides as active catalysts for the enantioselective Michael addition of aldehydes to beta-nitrostyrenes. The optimal anchor position and orientation between the catalyst and solid support, as well as the linker length, were carefully designed to enhance the catalytic efficiency. These supported catalysts exhibited high yields and enantiomeric excesses, and detailed deactivation studies provided important insights for prolonging their useful life.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Ryan T. Davison, Patrick D. Parker, Xintong Hou, Crystal P. Chung, Sara A. Augustine, Vy M. Dong
Summary: In this study, the coupling of alpha-nitroesters and alkynes using Rh-H catalysis was employed to prepare alpha-amino-acid precursors. This atom-economical strategy allows for the generation of two contiguous stereocenters with high enantio- and diastereocontrol. The alkyne undergoes isomerization to form a Rh-III-pi-allyl electrophile which then reacts with an alpha-nitroester nucleophile, ultimately leading to the formation of allylic alpha-amino esters through reduction with In powder.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Gianluca Casotti, Vincenzo Rositano, Anna Iuliano
Summary: Stabilised arylzinc iodide prepared by direct insertion of zinc into aryl iodides, were successfully applied as nucleophiles in the Hayashi Rh-catalysed enantioselective conjugate addition to enones, with high yields and 99% ee of the addition product. The general applicability of the protocol was confirmed by using different arylzinc iodides and enones, as well as organometallic reagents with both halogen and electrophilic groups.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Yiqi Ren, Maodi Wang, Qihua Yang, Junfa Zhu
Summary: The development of chiral solid catalysts using unconventional strategies is crucial for efficient heterogeneous asymmetric catalysis. The study presents a chiral solid catalyst, chiral diamine modified Ni/SiO2, for asymmetric Michael addition. The experimental results demonstrate that the peripheral Ni sites in close contact with SiO2 support are likely to be the active sites.
Article
Chemistry, Multidisciplinary
Sebastian Frankowski, Justyna Kowalska, Anna Albrecht
Summary: A novel method has been described for the preparation of enantiomerically enriched pyridine derivatives using 2-pyridylacetic acids as valuable synthons in an asymmetric fashion. The synthesis based on iminium activation using a chiral aminocatalyst successfully controlled the stereochemical outcome of the transformation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Tetsuya Ezawa, Yoshihiro Sohtome, Daisuke Hashizume, Masaya Adachi, Mai Akakabe, Hiroyuki Koshino, Mikiko Sodeoka
Summary: This study explores stereo-chemical dynamics in Ni(II)-catalyzed reactions, demonstrating a wide substrate scope and high selectivity in forming CN-containing building blocks with adjacent stereocenters. Computational investigations indicate that enantioselectivity is governed by the deprotonation process, while unique syn addition is controlled by noncovalent interactions between the nitrone and ligand.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Takahiro Moriyama, Daiki Mizukami, Makoto Yoritate, Kazuteru Usui, Daisuke Takahashi, Eisuke Ota, Mikiko Sodeoka, Tadashi Ueda, Satoru Karasawa, Go Hirai
Summary: Minimalist photo-reactive probes, consisting of a photo-reactive group and a tag for detection of target proteins, are valuable tools in chemical biology. In this study, minimalist probes based on a 2-thienyl-substituted alpha-ketoamide with an alkyne group on the thiophene ring were developed. The 3-alkyne probe showed the highest photo-affinity labeling efficiency.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Masumi Sugawara, Miki Sawamura, Mai Akakabe, Boobalan Ramadoss, Yoshihiro Sohtome, Mikiko Sodeoka
Summary: This study investigates the oxidative cross-dehydrogenative coupling reaction of monomers and dimers. The reactivity of the monomers is found to be lower than that of the dimers under aerobic conditions. The reactivity of the monomers can be significantly improved by using a modified catalyst, enabling them to undergo the oxidative cross-dehydrogenative coupling reaction with catechols.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Review
Biochemistry & Molecular Biology
Syusuke Egoshi, Kosuke Dodo, Mikiko Sodeoka
Summary: This article reviews the applications of Raman microscopy in deducing the distributions of endogenous biomolecules without exogenous labeling. It also discusses the use of deuterated fatty acids for lipid analysis and observing intracellular metabolic activities.
CURRENT OPINION IN CHEMICAL BIOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Kohei Toh, Kosuke Nishio, Reiko Nakagawa, Syusuke Egoshi, Masahiro Abo, Amelie Perron, Shin-ichi Sato, Naoki Okumura, Noriko Koizumi, Kosuke Dodo, Mikiko Sodeoka, Motonari Uesugi
Summary: Research has shown that visible light, especially in the blue region, can cause cell dysfunction and contribute to cellular aging and age-related pathologies by generating singlet oxygen. A chemoproteomic approach has been used to map blue-light-damaged proteins in live mammalian cells, revealing that cell surface proteins are more prone to oxidation compared to other susceptible proteins. The integrin family of cell surface receptors, including ITGB1, was found to be highly impacted, leading to loss of functionality in cell adhesion and proliferation. This study highlights the importance of understanding light-induced protein damages and their effects on cellular functions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Kosuke Dodo, Katsumasa Fujita, Mikiko Sodeoka
Summary: This article introduces the application of Raman spectroscopy in chemical biology research, including label-free Raman imaging of biomolecules and Raman imaging of small molecules using Raman tags. Raman probes represent the next-generation probes in chemical biology.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Applied
Shintaro Kawamura, Pablo Barrio, Santos Fustero, Jorge Escorihuela, Jianlin Han, Vadim A. Soloshonok, Mikiko Sodeoka
Summary: The difunctionalizative trifluoromethylation of unsaturated C-C bonds is a highly useful and efficient method for synthesizing trifluoromethyl compounds. This review focuses on reactions that simultaneously form C-heteroatom and C-H bonds, providing useful CF3 group-containing building blocks. The comprehensive survey categorizes reactions into those that are synthetically mature and those with room for further development.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Takuma Tagami, Yusuke Mitani, Shintaro Kawamura, Mikiko Sodeoka
Summary: Given the significance of difluoromethylated molecules in drug and agrochemical development, the establishment of synthetic protocols for their synthesis has gained much attention. This study reports a general and practical Cu-catalyzed method for the difluoromethylation of alkenes using difluoroacetic anhydride (DFAA) as a CF2H source. The reaction proceeds via the in situ generation of bis(difluoroacetyl) peroxide (BDFAP) from DFAA and H2O2. The obtained results enable the simple and efficient synthesis of a wide range of difluoromethylated species for their practical applications in medicinal and agricultural chemistry.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Kenji Hayamizu, Kota Koike, Kosuke Dodo, Miwako Asanuma, Hiromichi Egami, Mikiko Sodeoka
Summary: Palladium enolates derived from β-ketocarbonyl compounds are stable in air and moisture. This stability was utilized to develop a peptide purification system using β-ketoamide as a small affinity tag in aqueous media. A solid-supported palladium complex efficiently captured and released β-ketoamide-tagged molecules, allowing for the purification and identification of ligand-binding sites in proteins.
Article
Chemistry, Medicinal
Yoshihiro Sohtome, Mikiko Sodeoka
Summary: Researchers have found through computational analysis that the key steps in the synthesis of chiral molecules are regulated by multiple factors including isomerism of the complex, isomerism of the enolate, and spatial repulsion between reactants and ligands.
CHEMICAL & PHARMACEUTICAL BULLETIN
(2022)
Article
Biochemistry & Molecular Biology
Kazuki Sasaki, Michihiro Suzuki, Takeshi Sonoda, Tilman Schneider-Poetsch, Akihiro Ito, Motoki Takagi, Shinya Fujishiro, Yoshihiro Sohtome, Kosuke Dodo, Takashi Umehara, Hiroyuki Aburatani, Kazuo Shin-ya, Yoichi Nakao, Mikiko Sodeoka, Minoru Yoshida
Summary: This study developed an FRET-based probe that successfully traces dynamic changes in H3K9me3 and revealed subtle alterations that occur during mitosis.
CELL CHEMICAL BIOLOGY
(2022)
Article
Chemistry, Organic
Subrata Mukherjee, Shintaro Kawamura, Mikiko Sodeoka
Summary: Fluoroalkylation is an important strategy for enhancing the drug-like properties and bioactivities of compounds. This mini-review focuses on intramolecular difunctionalization-type fluoroalkylations of alkenes using Togni reagent and fluorine-containing carboxylic anhydrides. These reactions yield fluoroalkyl-group-containing carbo- and heterocycles as potential bioactive compounds.
Review
Biochemistry & Molecular Biology
Subha Bakthavatsalam, Kosuke Dodo, Mikiko Sodeoka
Summary: ATRI is a technique that utilizes alkyne functional groups for Raman imaging, allowing accurate visualization of molecular distribution in biological samples. Widely used in a variety of biological samples from organelles to whole animal models, this technique shows great potential for future development.
RSC CHEMICAL BIOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Go Hirai, Marie Kato, Hiroyuki Koshino, Eri Nishizawa, Kana Oonuma, Eisuke Ota, Toru Watanabe, Daisuke Hashizume, Yuki Tamura, Mitsuaki Okada, Taeko Miyagi, Mikiko Sodeoka
Summary: Glycoconjugates are important bio-molecules that regulate biological events in cells. This study successfully synthesized sialidase-resistant analogues of ganglioside GM3, demonstrating their inhibitory activity on EGF receptor autophosphorylation.
Article
Biochemistry & Molecular Biology
Mingming Chen, Miwako Asanuma, Mari Takahashi, Yuichi Shichino, Mari Mito, Koichi Fujiwara, Hironori Saito, Stephen N. Floor, Nicholas T. Ingolia, Mikiko Sodeoka, Kosuke Dodo, Takuhiro Ito, Shintaro Iwasaki
Summary: The translation inhibitor Rocaglamide A shows promising antitumor activity by clamping eIF4A and DDX3 onto polypurine RNA for selective translational repression. Analysis of a de novo-assembled transcriptome from the natural source of RocA, plant Aglaia, reveals the amino acid critical for RocA binding. The dominant-negative effect of RocA on eIF4A and DDX3 leads to strong translational repression in cancer cells, indicating its tumor toxicity.
CELL CHEMICAL BIOLOGY
(2021)
