Article
Chemistry, Multidisciplinary
Chuan-Wen Lei, Bo-Shuai Mu, Feng Zhou, Jin-Sheng Yu, Ying Zhou, Jian Zhou
Summary: The chemistry of carbocations has witnessed significant advances over the past 120 years, with current research focused on developing catalytic asymmetric reactions to overcome the intrinsic instability and high reactivity of prochiral carbocationic intermediates. Highly enantioselective protocols evolving prochiral carbocationic intermediates have been achieved through various strategies.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Beata Lukasik, Justyna Kowalska, Sebastian Frankowski, Lukasz Albrecht
Summary: A new umpolung approach has been developed for the asymmetric Friedel-Crafts-type alkylation of electron-poor heteroaromatic systems using hydrazones. The method shows excellent enantioselectivities under aminocatalytic conditions, and also provides a unique strategy for the asymmetric functionalization of electron-poor heteroaromatic systems.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Zeynep Dilsad Susam, Bilge Deniz Ozcan, Enis Kurtkaya, Erol Yildirim, Cihangir Tanyeli
Summary: In this study, bifunctional quinine-derived organocatalysts were used to catalyze the asymmetric Friedel-Crafts/S(N)2 domino reaction, resulting in enantiomerically enriched products. Density functional theory calculations were also performed to explain the stereoselectivity of the products.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Chemistry, Applied
Daniel Gavina, Marcos Escolano, Javier Torres, Gloria Alzuet-Pina, Maria Sanchez-Rosello, Carlos del Pozo
Summary: Substituted and annulated pyrroles containing chiral centers can be accessed through organocatalytic enantioselective Friedel-Crafts alkylation (FCA) reaction. These compounds are interesting due to their natural occurrence and diverse biological activities. In the past two decades, significant synthetic efforts have been made to develop asymmetric transformations involving pyrroles in the FCA reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Iryna D. Alshakova, Martin Albrecht
Summary: This research presents an efficient catalytic cascade process for the synthesis of triarylmethanes using a novel iridium catalyst. The method achieves efficient C-C coupling through reductive Friedel-Crafts alkylation, with high yields, excellent selectivities, and low iridium loadings. The catalytic activity of the system with hydride-proton coordination is significantly higher than that of other systems, demonstrating high catalytic performance.
Article
Chemistry, Organic
Xi Xiao, Xiaobiao Lu, Ming Zhang, Haoqing Hou, Changfeng Wan, Jinbiao Liu
Summary: A novel synthetic method was successfully developed for the preparation of multisubstituted dihydrochromeno[2,3-b]indole derivatives in moderate to high yields using a catalytic environmentally benign iron salt.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Takanori Shibata, Mio Sasaki, Masafumi Kojima, Mamoru Ito
Summary: The chiral Ir(I)-catalyzed intermolecular reaction of N-carbamoylpyrrole and indole derivatives with alpha,beta-unsaturated carbonyl compounds proceeded with high enantioselectivity, yielding chirally functionalized pyrroles and indoles as formal C-H conjugate adducts. The reaction mechanism was further investigated through deuterium labeling experiments.
Article
Chemistry, Multidisciplinary
Zhen Deng, Liu-Yan Qiu, Wenjie Pan, Baiyu Qian, Jie Chen, Hui Zhang, Qing-Yun Chen, Weiguo Cao, Xiao-Jun Tang
Summary: In this study, the classical Pummerer rearrangement efficiently produced S,O-acetal under specific conditions, and regenerated the reactive intermediate through the co-solvent, enabling the synthesis of 1-thiyl-2,2,2-trifluoroethyl arenes with excellent yields under metal-free conditions.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Organic
Hui Liu, Yingkun Yan, Min Li, Xiaomei Zhang
Summary: By utilizing chiral phosphoric acid as a catalyst, enantioselective aza-Friedel-Crafts reaction between 5-aminoisoxazoles and isatin-derived N-Boc ketimines was achieved, yielding novel 3-isoxazole 3-amino-oxindoles with high yields and moderate to good enantioselectivities. One product's absolute configuration was determined by X-ray crystal structural analysis, and a plausible reaction mechanism was proposed, followed by a successful scale-up reaction. Additionally, the product underwent Suzuki-Miyaura coupling with phenylboronic acid, resulting in moderate yield without affecting the enantioselectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Arben Berisa, Danijel Glavac, Chao Zheng, Shu-Li You, Matija Gredicak
Summary: An efficient enantioselective formal Betti reaction was described between phenols and diaryl ketimines generated in situ from isoindolinone alcohols. Catalyzed by a chiral phosphoric acid, a wide range of ketimines and phenols yielded isoindolinone derivatives with a congested quaternary stereogenic center bearing three aryl groups in high yields, regioselectivities, and enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Fan Xiao, Peiqin Liao, Xiaoguang Lu, Jin Wang, Xiu-Qin Dong, Chun-Jiang Wang
Summary: In this study, an Ir-catalyzed asymmetric cascade reaction was successfully developed for the synthesis of chiral oxazinoindolone compounds with high efficiency. The method can be applied to pyrroles and other nitrogen-containing aromatic heterocycles. The reaction pathway was proposed based on preliminary mechanistic investigation. Importantly, the key intermediate for marine alkaloid (+)-agelastatin A can be readily accessed using this methodology.
Article
Chemistry, Organic
Songjin Guo, Jiayi Chen, Mingjun Yi, Liuli Dong, Aijun Lin, Hequan Yao
Summary: A highly efficient synthesis of unsymmetrical 3,3'-diindolylmethanes has been developed by palladium-catalyzed cascade Heck/cyclization reaction, allowing for the formation of one C-N bond, two C-C bonds and two new rings in one-pot. Precursors allenamides and o-ethynylanilines were utilized to generate in situ indole skeletons, and modification of the methylene unit of diindolylmethane was achieved by treatment with oxidant and silyl nucleophiles.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Qian-Yi Wang, Teng-Fei Liu, Li-Feng Chu, Yun Yao, Chong-Dao Lu
Summary: In the presence of a chiral spiro phosphoric acid catalyst, the asymmetric reaction of disubstituted ketenes with N-H pyrroles occurred to afford enantioenriched C-acylated pyrroles bearing alpha-stereogenic carbon centres. This reaction represents a rare example of catalytic asymmetric reaction of ketenes with carbon-based nucleophiles, with significant research implications.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Bei Zhou, Zhuang Ma, Asma M. Alenad, Carsten Kreyenschulte, Stephan Bartling, Matthias Beller, Rajenahally Jagadeesh
Summary: A general method for cobalt-catalysed CH-alkylation of indoles with alcohols is reported, which allows the easy synthesis of substituted and functionalized indoles in good yields. The resulting products are an interesting class of heterocyclic compounds widely used in organic synthesis and medicinal chemistry.
Article
Chemistry, Physical
Hua-Qi Wang, Shu-Bin Mou, Wen Xiao, Huan Zhou, Xu-Dong Hou, Su-Jing Wang, Qian Wang, Jiali Gao, Zhiyi Wei, Lijun Liu, Zheng Xiang
Summary: CylK is a key enzyme that catalyzes the formation of the cylindrocyclophane scaffold through Friedel-Crafts alkylation reactions, exhibiting regioselectivity and stereospecificity. This study proposes a concerted double-activation mechanism to explain the enzymatic alkylation with regioselectivity and stereospecificity, based on crystal structures, free energy simulations, and site-directed mutagenesis experiments.
Review
Chemistry, Multidisciplinary
Yoshihiro Sohtome, Kyohei Kanomata, Mikiko Sodeoka
Summary: The review outlines the rapid expansion in the scope of cross-coupling reactions involving tertiary carbon-centered radicals over the past decade, with a focus on the reactivity and selectivity relationships of persistent tertiary carbon-centered radicals derived from carbonyl- or related compounds. Selected recent examples of cross-coupling reactions are presented to demonstrate their versatility as a synthetic tool for structural diversification of small molecules.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Chemistry, Multidisciplinary
Minami Odagi, Taisei Matoba, Keisuke Hosoya, Kazuo Nagasawa
Summary: The first enantioselective total syntheses of hasubanan alkaloid (-)-metaphanine and norhasubanan alkaloid (+)-stephadiamine have been reported. These syntheses involve diastereoselective oxidative phenolic coupling reaction and subsequent regioselective intramolecular aza-Michael reaction to efficiently construct the hasubanan skeleton with a quaternary stereogenic center at C13. Furthermore, based on a hypothesis regarding the biosynthetic pathway of (+)-stephadiamine, it was found that (-)-metaphanine can easily be converted to (+)-stephadiamine via an aza-benzilic acid type rearrangement reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Minami Odagi, Taisei Matoba, Kazuo Nagasawa
Summary: In this paper, we describe the enantioselective total syntheses of cepharatines A-D, which are members of the hasubanan alkaloid family and feature an unusual tetracyclic skeleton including an azabicyclo[3.3.1]nonane motif. The key reaction involves a regio-divergent oxidative phenolic coupling reaction that efficiently affords the tricyclic core structure of hasubanan with different substitution patterns on the A-ring, including the all-carbon quaternary stereogenic center at C13, in a single step. Furthermore, the characteristic tetracyclic azabicyclo[3.3.1]nonane motif is constructed via a bioinspired cascade reaction involving the retro-aza-Michael reaction/hemiaminal formation.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Yuka Mizumoto, Ryota Sakamoto, Akiko Nagata, Suzuka Sakane, Atsushi Kittaka, Minami Odagi, Masayuki Tera, Kazuo Nagasawa
Summary: This study synthesized 19-nor type 1,25D(3) derivatives with alkoxy groups at C2 and evaluated their biological activities in cell differentiation. The α-methoxy-substituted C2α-7a showed potent activity.
Article
Biochemistry & Molecular Biology
Yuka Iwasaki, Yurino Ookuro, Keisuke Iida, Kazuo Nagasawa, Wataru Yoshida
Summary: This study evaluates the effect of m(6)A modifications on G4 structures and finds that m(6)A modifications can destabilize certain G4 structures, potentially regulating biological functions.
BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Akiko Nagata, Kazuto Iijima, Ryota Sakamoto, Yuka Mizumoto, Miho Iwaki, Masaki Takiwaki, Yoshikuni Kikutani, Seketsu Fukuzawa, Minami Odagi, Masayuki Tera, Kazuo Nagasawa
Summary: This study describes a versatile method for synthesizing deuterium-labeled D-3 metabolites and successfully applies it to measure the concentration of these compounds in pooled human serum. This includes the first quantification of 1,25(OH)(2)D-3-23,26-lactone in human serum.
Article
Biochemistry & Molecular Biology
Anh Thi Tram Tu, Kazuaki Hoshi, Yue Ma, Taiji Oyama, Satoko Suzuki, Kaori Tsukakoshi, Kazuo Nagasawa, Kazunori Ikebukuro, Tomohiko Yamazaki
Summary: This study shows that using G4 ligands can increase the stability and function of G4 CpG ODNs, improving their immunostimulatory properties as vaccine adjuvants. Two different G4 ligands have different effects on the topology and stability of G4 CpG ODNs, and only GD3 associated with one G4 ligand can effectively activate immune response.
ACS CHEMICAL BIOLOGY
(2022)
Article
Biochemical Research Methods
Pravin Pokhrel, Shogo Sasaki, Changpeng Hu, Deepak Karna, Shankar Pandey, Yue Ma, Kazuo Nagasawa, Hanbin Mao
Summary: Binding between a ligand and a receptor is a fundamental step in many processes. We developed a single-molecule displacement assay to evaluate the binding of L2H2-6OTD ligands to human telomeric DNA G-quadruplexes, and found that dendrimer ligands have enhanced binding affinity.
ANALYTICAL BIOCHEMISTRY
(2022)
Article
Chemistry, Organic
Ryota Sakamoto, Minami Odagi, Atsuto Izumiseki, Kaname Konuki, Kazuo Nagasawa
Summary: In this study, we describe a versatile method for the synthesis of homoallenylboronic esters via lithiation-borylation and subsequent 1,2-rearrangement. The resulting homoallenylboronic esters can be successfully converted into Z- and E-1,3-dienes.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biology
Eriko Matsuura-Suzuki, Tadahiro Shimazu, Mari Takahashi, Kaoru Kotoshiba, Takehiro Suzuki, Kazuhiro Kashiwagi, Yoshihiro Sohtome, Mai Akakabe, Mikiko Sodeoka, Naoshi Dohmae, Takuhiro Ito, Yoichi Shinkai, Shintaro Iwasaki, Qing Zhang
Summary: In this study, it was discovered that human METTL18 acts as a histidine methyltransferase for the ribosomal protein RPL3. The methylation of RPL3 at His245 position slows ribosome traversal on Tyr codons, allowing proper protein folding and preventing cellular aggregation of Tyr-rich proteins.
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)
Article
Chemistry, Multidisciplinary
Yoshihiro Sohtome, Mikiko Sodeoka
Summary: Cross-dehydrogenative coupling (CDC) reaction is a powerful strategy for synthesizing carbon-carbon bonds, but its mechanisms are complex and not always intuitive. Therefore, understanding the key principles to selectively promote bond-forming events in CDC reactions is crucial for further development. This review focuses on the CDC reaction of benzene-1,2-diols, aiming to provide a comprehensive understanding of the complex bond-forming events. The reactions are classified into Type I and Type II mechanisms based on the mechanistic differences in the C-C bond formation. By describing the features of quinone redox reactions, the reactivity differences between benzene-1,2-diols and 1,2-benzoquinones are discussed. The historical background and current state of CDC reactions starting from benzene-1,2-diols are presented. This mini-review encourages the development of catalytic CDC reactions using benzene-1,2-diols and other substrates.
PURE AND APPLIED CHEMISTRY
(2023)
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
Biochemistry & Molecular Biology
Aileen Mendoza, Yasushi Takemoto, Kevin Tan Cruzado, Shadi Sedghi Masoud, Akiko Nagata, Ajcharapan Tantipanjaporn, Satoshi Okuda, Fumihiro Kawagoe, Ryota Sakamoto, Minami Odagi, Sayuri Mototani, Moeka Togashi, Makoto Kawatani, Harumi Aono, Hiroyuki Osada, Hayato Nakagawa, Tatsuya Higashi, Atsushi Kittaka, Kazuo Nagasawa, Motonari Uesugi
Summary: Lactone-vitamin D3, a major metabolite of vitamin D3, interacts with the mitochondrial enzyme HADHA and potentially regulates fatty acid 0-oxidation and carnitine biosynthesis. These findings provide new insights into sunlight-dependent shifts of lipid metabolism in animals.
CELL CHEMICAL BIOLOGY
(2022)
