Article
Chemistry, Organic
Kim Greis, Carla Kirschbaum, Giulio Fittolani, Eike Mucha, Rayoon Chang, Gert von Helden, Gerard Meijer, Martina Delbianco, Peter H. Seeberger, Kevin Pagel
Summary: This study investigates the influence of fluorination on the structure of the glycosyl cation, an intermediate in glycosylation reactions. The results reveal that C3 and C6 fluorination of glucosyl building blocks can alter the structure of the glycosyl cation, with neighboring group participation being the dominant motif.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Maziar S. Ardejani, Louis Noodleman, Evan T. Powers, Jeffery W. Kelly
Summary: The study demonstrates that stereoelectronic effects play a role in stabilizing protein-N-glycan interactions, with enthalpy-entropy compensation depending on the electronics of interacting side chains. Models using quantum mechanical calculations and machine learning can explain up to 79% and 97% of the experimental interaction energy variability.
Article
Chemistry, Organic
Caecilie M. M. Benckendorff, Chris S. Hawes, Mark Smith, Gavin J. Miller
Summary: This study reports the chemical diversification of carbocyclic pyrimidine nucleoside analogues containing CF2 and CHF, introducing ring unsaturation and 2'-epimers. By synthesizing gram-scale amounts of 6'-(R)-monofluoro and 6'-(R)-gem-difluoro-uridine, the provision of 2',3'-didehydro-2',3'-dideoxy and 1',2'-didehydro-2'-deoxy analogues, as well as a 6'-(R)-fluoro arabino-carbauridine, is explored. Key stereochemistries and unsaturation are confirmed using X-ray crystallography and NMR, and a conformational preference for a monofluoro 2',3'-didehydro-2',3'-dideoxy system is presented. This synthetic blueprint offers the potential to investigate the biological activity of previously unavailable materials and compare them directly to established nucleoside analogue drugs.
Article
Chemistry, Organic
Zoeisha S. Chinoy, Kelley W. Moremen, Frederic Friscourt
Summary: This study reports a new chemical tool, sydnone-aglycon, that can be used for the synthesis of O-glycans and the high-throughput screening of O-glycan-lectin interactions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Mei-Huei Lin, Jakob B. Wolf, Eric T. Sletten, Dario Cambie, Jose Danglad-Flores, Peter H. Seeberger
Summary: This article discusses the complexity of synthesizing defined oligosaccharides and introduces several enabling technologies that have been introduced in the past two decades to facilitate their synthesis. The application of automated glycan assembly, flow chemistry, and data science are highlighted as examples, emphasizing how the synergies between these technologies can further advance the field of glycochemistry.
Article
Chemistry, Multidisciplinary
Xian-Yang Zhou, Ling-Xin Li, Zhen Zhang, Shi-Chao Duan, Ying-Wen Huang, Yi-Yang Luo, Xiao-Dong Mu, Zhi-Wei Chen, Yong Qin, Jing Hu, Jian Yin, Jin-Song Yang
Summary: Acinetobacter baumannii poses a serious threat to global health, and its lipopolysaccharide (LPS) has been found to have antigenic properties. Research has identified a potential antigenic epitope in one of the branches of the LPS, which is attractive for the development of carbohydrate vaccines against A. baumannii.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Francesca Franco, Sara Meninno, Alessandra Lattanzi, Alessandra Puglisi, Maurizio Benaglia
Summary: A continuous flow approach was developed for the synthesis of alpha-trifluoromethylthiolated esters and amides using commercially available arylacetic acids and N-(trifluoromethylthio)phthalimide as the electrophilic reagent. The telescoped process resulted in good overall yield and short reaction times for the formation of alpha-substituted SCF3 amides and esters.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Daniel A. Decato, Jiyu Sun, Madeleine R. Boller, Orion B. Berryman
Summary: C-H hydrogen bonds have significant impacts on chemical systems, especially on iodine atoms. The introduction of a methyl group in the receptor leads to intramolecular C-H hydrogen bonding, which affects the binding conformation of the halogen bond donors. Experimental results show that methyl C-H hydrogen bonds bias the bidentate binding conformation and enhance the interaction energy of the halogen bond. Furthermore, receptors with C-H hydrogen bond enhanced halogen bonds exhibit improved performance in solution.
Review
Chemistry, Multidisciplinary
Yamei Lin, Jie Yu, Xing Zhang, Jingkun Fang, Guo-Ping Lu, He Huang
Summary: Porous carbon materials have gained significant attention in the field of organic synthesis due to their adjustable properties, excellent catalytic activity, and stability. Utilizing biomass-based carbohydrates as precursors for these materials is of great importance for sustainable development in organic chemistry. This review summarizes recent examples of carbohydrate-derived porous carbon materials catalyzing various organic reactions and provides insights into their preparation, functionalization strategies, as well as the challenges and opportunities in organic synthesis using these sustainable materials. It aims to stimulate further research in exploring novel carbohydrate-derived porous carbon materials and sustainable organic synthetic processes.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Lifeng Sun, Pradeep Chopra, Geert-Jan Boons
Summary: A new method for the synthesis of heparan sulfate oligosaccharides composed of unsulfonated fragments of different lengths was reported. Competition binding studies showed that the length of the unsulfonated fragment modulates the binding of chemokines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Chun-Wei Chang, Mei-Huei Lin, Chieh-Kai Chan, Kuan-Yu Su, Chia-Hui Wu, Wei-Chih Lo, Sarah Lam, Yu-Ting Cheng, Pin-Hsuan Liao, Chi-Huey Wong, Cheng-Chung Wang
Summary: The acceptor nucleophilic constants (Aka) database quantifies the nucleophilicity of hydroxyl groups in glycosylation reactions, accurately predicting stereoselectivity and yield.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Chun Tang, Xue-Lian Jiang, Shiyan Chen, Wenjing Hong, Jun Li, Haiping Xia
Summary: We investigated the charge transport through dx-px conjugated backbones with metal-carbon multiple bonds using the single-molecule break junction technique. The dx-px conjugation not only supports high conductivity but also enhances the tunable diversity in electronic properties through metal-induced secondary interaction. The introduction of the metal brings an unconventionally stereoelectronic effect, which can be modulated by protonation on the metal-carbon multiple bonds, affecting the single-molecule rectification feature and transmission mechanism. This work demonstrates the promise of utilizing the diverse electronic effect of metals to design molecular devices.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Chun Tang, Xue-Lian Jiang, Shiyan Chen, Wenjing Hong, Jun Li, Haiping Xia
Summary: In this study, the charge transport through dir-pir conjugated backbones with metal-carbon multiple bonds integrated into the alternative conjugated pathways was investigated using the single-molecule break junction technique. The introduction of metal induced a stereoelectronic effect through metal-carbon dir-pir hyperconjugation, which could be modulated by protonation on the metal-carbon multiple bonds, collectively altering the rectification feature and transmission mechanism of the single-molecule.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Yuexin Liu, Yang Jiao, Huajun Luo, Nianyu Huang, Mengnan Lai, Kun Zou, Hui Yao
Summary: An effective regiodivergent synthesis of 1- and 3-thiosugars was achieved using palladium and cobalt catalysis, respectively. The difference in the interaction of thiol moieties with Pd and Co catalysis conditions led to the selective formation of beta-1-thiosugars and (3S)-3-thiosugars. Experimental and theoretical calculations supported the proposed mechanism and provided insights into the regioselectivity based on the bond lengths of key intermediates.
Article
Chemistry, Multidisciplinary
Lea Spitzer, Sebastien Lecommandoux, Henri Cramail, Francois Jerome
Summary: An efficient method has been developed to synthesize end-functionalized oligosaccharides from unprotected monosaccharides, using a one-pot/two-step approach. The monosaccharides were first functionalized with an alkyne group at the anomeric position, then oligomerized to reach a DPn of up to 8. The obtained oligosaccharides showed complete propargylation and could be coupled to oleic acid to produce bio-based surfactants.
