Article
Chemistry, Multidisciplinary
Anselme Geulin, Yann Bourne-Branchu, Kawther Ben Ayed, Thomas Lecourt, Antoine Joosten
Summary: 3-Amino-3-deoxyglycosides are important nitrogen-containing sugars, with many important ones having a 1,2-trans configuration. The synthesis of 3-amino-3-deoxyglycosyl donors that can form a 1,2-trans glycosidic linkage is a significant challenge due to their biological applications. This work presents a new sequence involving Ferrier rearrangement and subsequent aza-Wacker cyclization for the rapid synthesis of orthogonally protected 3-amino-3-deoxyglycals. Additionally, the epoxidation/glycosylation of a 3-amino-3-deoxygalactal derivative was successfully achieved with high yield and diastereoselectivity, demonstrating FAWEG as a new approach for accessing 1,2-trans 3-amino-3-deoxyglycosides.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Levente Homolya, David Antal, Mate Nagy, Eva Juhasz-Toth, Marietta Toth, Attila Benyei, Laszlo Somsak, Laszlo Juhasz
Summary: The reactivity of O-peracetylated and O-perbenzoylated 1-COOMe, 1-CONH2 and 1-CN-substituted glycals against O-, S-, N-, and C-nucleophiles in the presence of Lewis acids was investigated. The results showed that the stereoselectivity of the formed products varied with different nucleophiles.
CARBOHYDRATE RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Naresh Bhuma, Ludivine Lebedel, Hiroki Yamashita, Yutaka Shimizu, Zahra Abada, Ana Arda, Jerome Desire, Bastien Michelet, Agnes Martin-Mingot, Ali Abou-Hassan, Masahiro Takumi, Jerome Marrot, Jesus Jimenez-Barbero, Aiichiro Nagaki, Yves Bleriot, Sebastien Thibaudeau
Summary: Ferrier's research in 1962 on the transformation of glycals into unsaturated glycosyl derivatives involved an alpha,beta unsaturated glycosyl cation. Through NMR-based structural analysis and DFT calculations, this elusive ionic species was characterized, leading to the synthesis of unsaturated nitrogen-containing C-aryl glycosides and C-alkyl glycosides under different conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Kim Greis, Caleb E. Griesbach, Carla Kirschbaum, Gerard Meijer, Gert von Helden, Kevin Pagel, Mark W. Peczuh
Summary: Ferrier reactions involve Lewis acid activation of a cyclic enol ether to generate a glycosyl Ferrier cation through the departure of an allylic leaving group. The resulting cation undergoes attack and transposition, forming a new acetal linkage. This study focuses on the septanosyl Ferrier cation derived from a seven-membered ring carbohydrate-based oxepine. Experimental characterization of the ion, including gas-phase cryogenic IR spectroscopy and solution-phase Ferrier reactions, reveals a preference for contraction to five-membered ring structures in the cation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Yogesh Yadav, Rajdeep Tyagi, Kanchan Yadav, Ghanshyam Tiwari, Ram Sagar
Summary: The Ferrier rearrangement using SnCl4 as catalyst allows for the synthesis of 2,3-unsaturated glycopyranosides with high stereoselectivity starting from the hydroxyl group at the C-3 position. This method has several advantages, including strong anomeric selectivity, high yields, and short reaction time.
CARBOHYDRATE RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Zhao-Xiang Luo, Miao Liu, Tian Li, De-Cai Xiong, Xin-Shan Ye
Summary: In this study, a convenient one-step electrochemical bromination of glycals was achieved using Bu4NBr as the brominating source under metal-catalyst-free and oxidant-free conditions. A series of 2-bromoglycals were successfully synthesized and further used in coupling reactions to efficiently produce 2C-branched carbohydrates and disaccharides. Radical trapping and cyclic voltammetry experiments suggested the involvement of bromine radicals in the reaction process.
FRONTIERS IN CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Zhiqiang Lu, Yanzhi Li, Shaohua Xiang, Mengke Zuo, Yangxing Sun, Xingxing Jiang, Rongkai Jiao, Yinghong Wang, Yuqin Fu
Summary: The use of perfluorinated solvent in the stereoselective formation of O-/S-glycosidic linkages via a Ferrier rearrangement of acetylated glycals has been demonstrated for the first time. This method shows enhanced reactivity and stereocontrol through weak interactions with substrates, and it is environmentally friendly with low toxicity, easy recovery of the medium, and simple product isolation.
Article
Chemistry, Organic
Agustin H. Rojas, Leticia Lafuente, Virginia Vetere, Agustin Ponzinibbio
Summary: This study presents the selective synthesis of new 2-iodo-2,3-unsaturated O- and S-glycosides, marking the first report on the Ferrier rearrangement of 2-halo-glycals with S-nucleophiles. The alpha-glycosides were obtained in good yields and with high anomeric selectivity. Additionally, the particular behavior of heteroaromatic thio sugar derivatives, including an alternative mechanism for C3 addition, was described, with a complete structure and conformation analysis provided by NMR.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Rajendra K. Mallick, Srinivas Vangara, Nagarjuna Kommu, Tirumaleswararao Guntreddi, Akhila K. Sahoo
Summary: This paper describes a novel Cu(II)-catalyzed rearrangement reaction for the synthesis of a series of synthetically important α-(m-substituted phenol)-α,β-unsaturated ketones, with a wide scope of functional group tolerance and synthetic viability. The synthesis of α,β-unsaturated ketones is also demonstrated in this study.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Rupa Bai Addanki, Suvendu Halder, Pavan K. Kancharla
Summary: This study demonstrates the application of strained and bulky protonated TTBPy triflate salt as a mild and efficient organocatalyst in diastereoselective C-Ferrier glycosylation, and reveals the importance of the trapped H2O molecule in the catalyst. The mechanism involves unique anionic triflate and H2O hydrogen-bond interactions that activate allylsilanes, providing unprecedented access to diastereoselective phenylallyl Ferrier glycosides.
Article
Chemistry, Multidisciplinary
Shintaro Ishida, Kengo Sakamoto, Ryo Kobayashi, Takeaki Iwamoto
Summary: This study reports the reactions of silanone with triarylboranes to form boroxysilanes. Experimental results and computational studies show that the electrophilicity of the unsaturated silicon atom is enhanced by the complexation of silanone with triarylboranes, and subsequent aryl migration from the boron atom to the electrophilic silicon atom takes place.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yuya Tsutsui, Daiki Tanaka, Yoshiyuki Manabe, Yuka Ikinaga, Kumpei Yano, Koichi Fukase, Akihito Konishi, Makoto Yasuda
Summary: We describe the synthesis and characterization of a photoactivated boron-based Lewis acid catalyst with a cage-shaped triphenolic ligand and three pyrenylmethyl moieties. This catalyst functions as a photoactivated Lewis acid catalyst due to the flexible three pyrenylmethyl moieties, which drive the deformation of the cage-shaped scaffold through intramolecular excimer formations of the pyrenes. Mannich-type reactions and glycosylations are significantly accelerated under 370 nm light irradiations. Notably, various glycosyl fluorides, which are not easily activated in photocatalytic systems, can be activated by the improved catalytic activity of this catalyst.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Hajime Maeda, Saki Nakamura, Taniyuki Furuyama, Masahito Segi
Summary: The reaction of 1-naphthyl naphthylmethyl ethers 1 and 2 with Lewis acids in CH2Cl2 resulted in rearrangement of the naphthylmethyl group to different positions of the naphthalene ring. The rearrangement of 2-naphthyl ethers 3 and 4 proceeded to the 1-position. Irradiation of compound 1 in benzene solution led to rearrangement at the 4-position, while rearrangement of compound 2 occurred at the 2- and 4-positions. The regioselectivity of the reactions can be explained by charge density, spin density, steric hindrance, and solvent cage effect.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Applied
Xin Jin, Rusi Peng, Wen Tong, Jinpeng Yin, Hao Xu, Peng Wu
Summary: In the Beckmann rearrangement, TS-1 exhibits superior catalytic performance with silanol groups (including terminal silanols, hydrogen-bonded silanols, and silanol nests) as the active centers. Monolithic TS-1 microspheres (M-TS-1) show higher catalytic activity compared to conventional TS-1, and the diffusion properties of M-TS-1 can be further improved through chemical modifications to achieve longer reaction lifetime.
Article
Multidisciplinary Sciences
Tana Tana, Pengfei Han, Aidan J. Brock, Xin Mao, Sarina Sarina, Eric R. Waclawik, Aijun Du, Steven E. Bottle, Huai-Yong Zhu
Summary: 5-hydroxymethylfurfural (HMF) is a valuable platform chemical for sustainable fine-chemical and pharmaceutical industry based on biomass. The complex of fulvic acid with Al3+ ions exhibits solar absorption and photocatalytic activity for glucose conversion to HMF in one-pot reaction, offering prospects for new green photocatalytic systems. This mechanism creates the possibility of synthesizing a range of substances that have not previously been considered.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Paramathevar Nagaraj, Namakkal G. Ramesh
Article
Biochemical Research Methods
P. Nagaraaj, V. Vijayakumar
JOURNAL OF FLUORESCENCE
(2019)
Article
Chemistry, Physical
K. Kalanidhi, P. Nagaraaj, C. A. Aswathy, G. Vanthana Sree
CHEMICAL PHYSICS LETTERS
(2020)
Article
Chemistry, Physical
V. Vijayakumar, A. Karuppusamy, P. Kannan, P. Nagaraaj
CHEMICAL PHYSICS LETTERS
(2020)
Article
Green & Sustainable Science & Technology
G. Vanthana Sree, P. Nagaraaj, K. Kalanidhi, C. A. Aswathy, P. Rajasekaran
JOURNAL OF CLEANER PRODUCTION
(2020)
Article
Chemistry, Organic
P. Rajamani, V. Vijayakumar, P. Nagaraaj, N. Sundaraganesan
Summary: This study focuses on the synthesis and characterization of a compound through Mannich type reaction, and the molecular properties were investigated using various analytical techniques. Computational studies were conducted to gain insights into the molecular structure and properties, and molecular docking studies revealed potential interactions between the compound and influenza and chikungunya protease enzymes.
POLYCYCLIC AROMATIC COMPOUNDS
(2022)
Article
Chemistry, Physical
K. Kalanidhi, P. Nagaraaj
Summary: In this study, water soluble nitrogen-doped carbon dots were synthesized from betel leaves using a hydrothermal method, showing excellent water solubility, biocompatibility, and stability. The carbon dots exhibited a strong response to picric acid and Fe3+ ions, allowing for the design of a dual detection system with high selectivity and sensitivity. This fluorescent probe has the potential to be a promising tool for sensitive detection of PA and Fe3+ in aqueous solutions.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2021)
Article
Materials Science, Multidisciplinary
K. Kalanidhi, P. Nagaraaj, Bharathi Mohan
Summary: In this study, waste engine oil was used to synthesize carbon dots (CDs) with excellent fluorescence properties for the first time. The synthesized CDs showed high water solubility, photostability, and biocompatibility, making them suitable for applications in detection and information storage.
DIAMOND AND RELATED MATERIALS
(2022)
Article
Chemistry, Applied
G. Ashok Varman, K. Kalanidhi, P. Nagaraaj
Summary: A simple, sustainable, and economically feasible approach has been reported for the synthesis of Carbon Dots (CDs) using Canon Ball (CB) fruit as a biomass precursor. The synthesized CDs exhibit excellent optical properties, stability, and can selectively detect Fe3+ ions and catalytically reduce harmful textile dyes.
Article
Chemistry, Physical
K. Kalanidhi, P. Nagaraaj
Summary: The use of N-doped carbon dots (NCDs) as a strengthening agent for advanced packaging materials has been explored. By incorporating NCDs into chitosan-PVP film through a simple solution casting method, the film's mechanical properties and biodegradability have been improved. The addition of orange peel extract enhances the performance of the film while also exhibiting good degradation ability and promoting plant growth.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Materials Science, Multidisciplinary
G. Vanthana Sree, P. Nagaraaj
Summary: This study repurposed waste materials like eggshells as nanofillers for PVA polymer, enhancing its stability and physical and chemical properties. The water-resistance and degradation ability of the films were studied, along with the impact of solubilized polymer solutions on soil and plant growth.
MATERIALS CHEMISTRY AND PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
S. Saravanan, Rafiq Ahmad, S. Kasthuri, Kunal Pal, S. Raviteja, P. Nagaraaj, Richard Hoogenboom, Venkatramaiah Nutalapati, Samarendra Maji
Summary: The development of a functionalized polymer for detecting nitroaromatics, with high selectivity and sensitivity, via fluorescence studies has been demonstrated. The polymer showed exceptional selectivity and a high quenching rate for 2,4,6-trinitrophenol. The research suggests that the polymer has potential for practical applications.
MATERIALS CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Organic
Muthupandian Ganesan, Paramathevar Nagaraaj
ORGANIC CHEMISTRY FRONTIERS
(2020)
Review
Chemistry, Analytical
Muthupandian Ganesan, Paramathevar Nagaraaj
ANALYTICAL METHODS
(2020)
Review
Chemistry, Organic
P. Nagaraaj, V. Vijayakumar
ORGANIC CHEMISTRY FRONTIERS
(2019)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
