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, Applied
Jing Huang, Bo Jiang, Xiyuan Zhang, Yanfeng Gao, Xiufang Xu, Zhiwei Miao
Summary: A synthetic strategy for accessing functionalized azabicyclo[3.3.1]alkenones with three tertiary stereocenters has been developed. The method is scalable and the products can be transformed to various eight-membered-ring bridged heterocyclic molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Fuzhu Yang, Wu Hou, Dapeng Zhu, Yu Tang, Biao Yu
Summary: A robust glycosylation protocol for the synthesis of 1,2-trans-beta-D- or alpha-L-glycosidic linkages without resorting to neighboring participation groups has been developed, demonstrating high yielding and exclusive 1,2-trans selectivity with a broad substrate scope.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Fuzhu Yang, Wu Hou, Dapeng Zhu, Yu Tang, Biao Yu
Summary: A robust glycosylation protocol has been developed for the synthesis of 1,2-trans-beta-d- or alpha-l-glycosidic linkages without the need for neighboring group participation. The method demonstrated a broad substrate scope and high selectivity in glycosylation reactions, leading to the successful synthesis of various triterpene saponins.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Teng Wang, Zhangyu Yu, Tao Liu
Summary: The reaction mechanisms of palladium-catalyzed oxidative cascade carbocyclization of enallene were investigated through density functional theory calculations, revealing that the diastereoselectivity is determined by weak interactions. The pathway with CO insertion prior to olefin insertion leading to the six-membered product was found to be unfavorable, consistent with experimental observations, and this regioselectivity is attributed to a combined electronic and steric effect.
MOLECULAR CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Krystyna M. Demkiw, Wouter A. Remmerswaal, Thomas Hansen, Gijsbert A. van der Marel, Jeroen D. C. Codee, K. A. Woerpel
Summary: This study found that acetal substitution reactions of alpha-halogenated five- and six-membered rings can exhibit high stereoselectivity, but this stereoselectivity diminishes as nucleophilicity increases. Computational investigations confirmed that open-form oxocarbenium ions are the reactive intermediates involved, and that hyperconjugative effects and through-space electrostatic interactions contribute to the stabilization of halogen-substituted oxocarbenium ions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Dmitriy D. Karcev, Mariia M. Efremova, Alexander P. Molchanov, Nikolai Rostovskii, Mariya A. Kryukova, Alexander S. Bunev, Dmitry A. Khochenkov
Summary: In this study, new highly functionalized 5-spiroisoxazolidines were synthesized through the 1,3-dipolar cycloaddition reaction, which showed good selectivity. The reversibility of these reactions allows for controlling the diastereoselectivity of cycloaddition. Additionally, the reduction reaction of the obtained adducts provides 1,3-aminoalcohols or spirolactones.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Organic
Natsuhisa Oka, Kanna Suzuki, Ayumi Mori, Kaori Ando
Summary: This study presents a highly stereoselective synthesis method for heteroaryl-substituted 1,2-cis-glycosyl sulfones, along with the investigation of one-pot Julia olefination using these sulfones. The results demonstrate the formation of thermodynamically less stable (E)-exo-glycals with E/Z selectivity of up to 91:9.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Huamin Wang, Mingming Yu, Panyue Zhang, Hao Wan, Hengjiang Cong, Aiwen Lei
Summary: This study investigates a strategy for synthesizing α-chlorosulfoxides using electrochemistry, which offers a broad substrate scope, high selectivity, and regionality, and can be applied to the late-stage modification of amino acids and pharmaceutical derivatives.
Article
Chemistry, Multidisciplinary
Chun-Wei Chang, Mei-Huei Lin, Cheng-Chung Wang
Summary: This article discusses the application of chemical synthesis in accessing carbohydrate-based natural products and derivatives, focusing on the challenge of stereoselectivity during the glycosylation reaction. Recent mechanistic studies applying statistical analysis and quantitation to define stereoselective changes during the reaction process are highlighted, with detailed discussions on the mechanisms and factors influencing the stereoselective outcome of glycosylation based on experimental evidence.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jin-Cai Lei, Yuan-Yuan Jiang, Yi-Fei Xia, Qing Fang, Shi-Chao Duan, Yu-Xiong Ruan, Jin-Song Yang
Summary: An efficient synthesis of a complex tetrasaccharide fragment 1 structurally related to rhamnogalacturonan II side chain A has been accomplished through a stepwise glycosylation strategy.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Gael M. Vos, Yunfei Wu, Roosmarijn van der Woude, Robert P. de Vries, Geert-Jan Boons
Summary: This paper introduces a chemo-enzymatic strategy for synthesizing poly-N-acetyl lactosamines (polyLacNAc) in a regioselective manner. The strategy involves enzymatic assembly of oligo-LacNAc chains and modification at specific positions using traceless blocking groups. The methodology allows for the synthesis of polyLacNAc chains with various topologies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Ruslana S. Khodzhaieva, Eugene S. Gladkov, Alexander Kyrychenko, Alexander D. Roshal
Summary: This mini-review summarizes the recent developments in flavonoid glycosylation, including reaction conditions, choice of glycosyl donor moiety, and regioselective glycosylation strategies for flavonoids with multiple hydroxyl groups.
FRONTIERS IN CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Kazuki Inaba, Yuna Naito, Mina Tachibana, Kazunobu Toshima, Daisuke Takahashi
Summary: A regioselective and beta-stereospecific d-/l-arabinofuranosylation method has been developed for efficient synthesis of biologically active natural glycosides. The method showed high regioselectivity and yield with complete beta-stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Min Zhang, Yuqi Ji, Chun Zhang
Summary: This review summarized the researches on the asymmetric chain-walking reactions catalyzed by transition metal in the past decade, classified according to the species of metal catalysts.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Natasha Videcrantz Faurschou, Christian Marcus Pedersen
Summary: Self-promoted glycosylations, although having the advantages of being easy to perform and highly stereoselective, have not received much attention. This field focuses on the mechanistic aspects of self-promoted glycosylations and the stereoselectivity of reactions, along with discussing examples of reactions with different donors. The strategies of self-promoted glycosylations can serve as a foundation for new stereoselective glycosylation methodologies.
Article
Chemistry, Multidisciplinary
Xueke Gao, Minjun Ma, Christian Marcus Pedersen, Rui Liu, Zhenzhou Zhang, Honghong Chang, Yan Qiao, Yingxiong Wang
Summary: This study investigated the interactions between 6-MP and PAMAM-NH2 using various NMR technologies, revealing that the interaction mechanism mainly involves electrostatic interactions and encapsulation of 6-MP within the cavity of PAMAM-NH2. The binding strength between 6-MP and PAMAM-NH2 was quantitatively expressed using epitope maps. This research provides a systematic methodology for qualitative and quantitative studies of the interactions between dendrimers and drug molecules.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Organic
Patrycja Mala, Christian Marcus Pedersen
Summary: N-Glycosyl N-sulfonyl amides were synthesized using self-promoted glycosylation without the need for catalysts or additives. The method allows for the selective beta-glycosylation of sulfonylated asparagine derivatives, providing access to glycosyl sulfonyl amides under mild conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Michael Martin Nielsen, Thomas Holmstrom, Christian Marcus Pedersen
Summary: Despite being relatively inaccessible to non-specialists, the field of carbohydrate chemistry is aiming to increase the availability of stereoselective glycosylation chemistry, through the discovery of commercially available pyrylium salts as catalysts. These catalysts have shown to enable stereoselective O-glycosylations of a wide range of phenols and alkyl alcohols, providing better reproducibility for non-specialists. The reaction exhibits varying degrees of stereospecificity and likely proceeds via an S(N)2-like substitution mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Nora Katharina Korber, Christian Marcus Pedersen
Summary: In this study, we demonstrated that both lithium and the respective counterions play a role in the activation of trichloroacetimidate glycosyl donors at room temperature. The glycosylations carried out under these mild conditions were slow and completed in two to eight days, with the rate and yield of the reaction being dependent on the counterion. However, the selectivity of all investigated lithium salts was found to be deficient.
CARBOHYDRATE RESEARCH
(2022)
Article
Chemistry, Organic
Mikael Bols, Tobias Gylling Frihed, Martin Jaeger Pedersen, Christian Marcus Pedersen
Summary: Silicon has been used as a protective group for sugar alcohols in carbohydrate chemistry for fifty years, but its usage has expanded recently to include C-H activation functionalization, conformational modification of glycosyl donors, and alteration of carbohydrate conformations. The influence of silicon extends beyond just protection, affecting the reactivity of glycosyl donors and the stereochemistry of glycosylations. Direct attachment of silicon to the sugar C-backbone has pronounced effects on the chemistry and properties of molecules.
Article
Chemistry, Physical
Zhaohui Guo, Chunyan Chen, Jiancheng Zhao, Xiaoya Guo, Lingyu Jia, Pengfei Liu, Christian Marcus Pedersen, Xianglin Hou, Yan Qiao, Yingxiong Wang
Summary: This study proposed a method for the conversion of N-acetyl-D-glucosamine to 3-acetamido-5-acetylfuran using boric acid and 1-allyl-3-methylimidazolium chloride catalyst. The mechanism was investigated using primary nuclear magnetic resonance technology, and the catalytic interactions were studied through chemical shift titration and mass spectroscopy.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Biochemistry & Molecular Biology
Liang Yang, Christian Marcus Pedersen
Summary: Protected 2-O-benzyolated glycosyl formates were synthesized in one-step from the corresponding orthoester using formic acid as the sole reagent. Glucopyranosyl, mannopyranosyl and galactopyranosyl donors were synthesized and their glycosylation properties were studied. Bismuth triflate was the preferred catalyst and KPF6 was used as an additive. The glycosylations showed excellent 1,2-trans-selectivities and high yields.
Review
Chemistry, Organic
Hang Su, Christian Marcus Pedersen
Summary: In recent years, the development of stimuli-responsive systems for targeted therapy has gained significant attention. However, the complexity of material preparation has been a challenge. This review focuses on the use of ring-system-based conformational switches in sensors and smart drug-delivery systems, highlighting their potential in simplifying material preparation.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Benedicte Ronne Kristensen, Christian Marcus Pedersen
Summary: A self-promoted glycosylation method was developed to selectively form beta-glucosides from a diverse substrate library. This two-component reaction occurs at elevated temperatures without the need for additives or catalysts, providing easy access to glycoconjugates under mild conditions. The influences of neighboring group participation and substituents were investigated, and kinetic data from in situ IR were used for a Hammett study, revealing a correlation between acceptor pK(a) and reaction rate and providing new mechanistic insights.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhaohui Guo, Christian Marcus Pedersen, Honghong Chang, Yingxiong Wang, Yan Qiao
Summary: Fructose is a renewable resource that is significant in biomass conversion and food industries. The combination of CaCl2 and Et3N was found to alter the thermodynamic equilibrium and promote fructose separation, resulting in a high yield of up to 78%. The formation of the α-fructofuranose complex shifted the equilibrium of glucose isomerization towards fructose formation, allowing for the production of high-purity fructose.
Article
Chemistry, Multidisciplinary
Natasha Videcrantz Faurschou, Rolf Hejle Taaning, Christian Marcus Pedersen
Summary: A novel approach for optimizing reactions in carbohydrate chemistry is introduced, utilizing Bayesian optimization to achieve regioselective benzoylation of unprotected glycosides. The optimization process includes 6-O-monobenzoylations and 3,6-O-dibenzoylations of three different monosaccharides. Moreover, a transfer learning method is developed to expedite the optimization process by leveraging data from previous optimizations of diverse substrates. The results from the Bayesian optimization algorithm reveal new insights into substrate specificity, with significantly different conditions found. Notably, the optimal conditions involve the use of Et3N and benzoic anhydride, a novel reagent combination discovered by the algorithm, showcasing the potential of this concept to expand the chemical space. Additionally, the developed procedures offer the advantages of ambient conditions and short reaction times.
Article
Chemistry, Physical
Yingqing Zhao, Rui Liu, Christian Marcus Pedersen, Zhenzhou Zhang, Zhaohui Guo, Honghong Chang, Yingxiong Wang, Yan Qiao
Summary: This study investigates the mechanism and catalytic interaction of the basic catalyst Ba(OH)(2) in the conversion of D-glucose into lactic acid. Experimental results reveal that the catalyst exists in the form of [Ba(OH)(H2O)(2)]+ and forms a complex D-glucopyranose-[Ba(OH)(D2O)(2)]+ with D-glucose. Surprisingly, lactic acid undergoes deuteration when the reaction is performed in D2O.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Review
Chemistry, Multidisciplinary
Michael Martin Nielsen, Christian Marcus Pedersen
Summary: In synthetic chemistry, the choice of reaction vessel material is often overlooked but can have a significant impact on the outcome of the chemical transformation. This review highlights the examples of vessel effects during chemical transformations and the container-dependent stability of certain molecules, encompassing various fields of chemistry.
Article
Chemistry, Organic
Yang Liang, Christian M. Pedersen
Summary: The introduction of chlorinated ethyl and vinyl ethers at various positions of carbohydrates results in the formation of vinylethers, acetals or orthoesters under basic conditions. The products are stable but easily deprotected after dechlorination. The scope of intramolecular protection is studied using common pentoses and hexoses.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
