Article
Chemistry, Multidisciplinary
Xiaoqian Li, Zhi Ma, Rongkun Liu, Mattan Hurevich, You Yang
Summary: A green and efficient photolabile protecting group (PPG)-mediated glycosidation approach for the synthesis of 2-deoxy-glycosides is reported. Multiple oNBC groups in the 2-deoxy-glycosides can be completely cleaved by irradiation at 365 nm, resulting in the desired 2-deoxy-glycosides in an efficient manner. Oligosaccharides with three to six oNBC groups are effectively achieved based on this PPG-mediated glycosidation approach.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hao Zuo, Chen Zhang, Yang Zhang, Dawen Niu
Summary: A simple and general method for fully unprotected, stereoselective glycosylation of carboxylic acids was developed using bench-stable allyl glycosyl sulfones as donors. The reaction, conducted under basic conditions, showed high efficiencies and selectivities. Both the donor activation stage and the glycosidic bond forming stage were compatible with free hydroxyl groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Correction
Chemistry, Multidisciplinary
Gao-Lan Zhang, Madhusudhan Reddy Gadi, Xikai Cui, Ding Liu, Jiabin Zhang, Varma Saikam, Christopher Gibbons, Peng G. Wang, Lei Li
Summary: The study presents a protection-group-free method for S-glycosylation, which can be applied in the synthesis of thioglycosides and thioglycopeptides in water.
Article
Biochemistry & Molecular Biology
Yu Hamaya, Naoko Komura, Akihiro Imamura, Hideharu Ishida, Hiromune Ando, Hide-Nori Tanaka
Summary: A protecting-group-free method for the synthesis of 0-glycosyl esters and aryl 0-glycosides was developed using the latent chemical reactivity of N-acetyl-D-glucosamine (GlcNAc) oxazoline. The method exhibits a wide substrate scope, good functional group tolerance, and can efficiently produce a novel class of GlcNAc-conjugated biomaterials and prodrug candidates.
BIOORGANIC & MEDICINAL CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Shogo Hamajima, Naoko Komura, Hide-Nori Tanaka, Akihiro Imamura, Hideharu Ishida, Tsuyoshi Ichiyanagi, Hiromune Ando
Summary: Chemical synthesis of Kdo-containing glycans is important for developing vaccines against pathogenic bacteria. The alpha-stereoselective glycosidation of Kdo has been achieved using a macrobicyclic donor. In this study, the protection of the 4-OH group and the use of a selectively removable booster allowed the synthesis of the dimeric Kdo sequence.
Article
Biochemistry & Molecular Biology
Yoshiyasu Ichikawa, Daisuke Kaneno, Nobuyoshi Saeki, Takahiro Minami, Toshiya Masuda, Kumi Yoshida, Tadao Kondo, Rika Ochi
Summary: The first protecting group-free synthesis of N-glycosyl carbamates was achieved by reacting D-glucose with n-butyl carbamate in acidic aqueous media. The structures of the N-glucosyl carbamates were determined by comparison with authentic samples, and an anomeric pair of N-xylopyranosyl carbamates were prepared to assess the anomeric effect of nitrogen in the carbamate group.
CARBOHYDRATE RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Ariza Khanam, Pintu Kumar Mandal
Summary: A convenient and highly efficient method has been developed for the stereoselective synthesis of N-glycofuranosyl and glycofuranosyl sulfonamides under catalyst and additive-free conditions. The two-component reaction proceeded smoothly with good yield and beta-stereoselectivity, allowing for further functionalization of the N-glycosides through selective deprotection of N-carbamates and N-sulfonyl groups.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Debashis Dhara, Laurence A. Mulard
Summary: The stereoselective synthesis of S. sonnei oligosaccharides comprising two, three and four repeating units is reported for the first time in this study. The use of multiple protecting groups and a specific building block design enabled the successful iterative glycosylation and deprotection steps.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Yoshiyuki Manabe, Takuya Matsumoto, Yuka Ikinaga, Yuya Tsutsui, Shota Sasaya, Yuichiro Kadonaga, Akihito Konishi, Makoto Yasuda, Tomoya Uto, Changhao Dai, Kumpei Yano, Atsushi Shimoyama, Ayana Matsuda, Koichi Fukase
Summary: The study found that catalytic glycosylations using BF3·Et2O could efficiently proceed without the use of dehydrating agents, in contrast to traditional reactions requiring excess Lewis acid and additives. Mechanistic studies showed that chemical species formed by the reaction of in situ generated HF and glass vessels are involved in the catalytic cycle.
Article
Chemistry, Organic
Mosidur Rahaman Molla, Rima Thakur
Summary: A new readily synthesized orthogonal protecting group, cyanomethyl (CNMe) ether, has been reported for efficient protection of saccharides with easy removal.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Gefei Li, Masato Noguchi, Masaki Ishihara, Yuka Takagi, Marina Nagaki, Sachie Saito, Masashi Saito, Xin-shan Ye, Shin-ichiro Shoda
Summary: Chemical O-glycosylation is crucial for synthesizing sugar-containing molecules like glycolipids. However, traditional carbohydrate chemistry involves extensive use of protective groups, which is time-consuming and inefficient. In this study, a protecting-group-free glycosylation strategy using DBT-glycosides as glycosyl donors was developed. The method allows for direct synthesis of DBT-glycosyl donors from unprotected sugars in water. O-glycosylation of alcohols using DBT-glycosyl donors under mild hydrogenolytic conditions resulted in stereo-selective formation of alkyl glycosides with high yields.
CARBOHYDRATE RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Xu Ma, Yongliang Zhang, Xijun Zhu, Yongliang Wei, Liming Zhang
Summary: This work introduces a novel catalytic S(N)2 glycosylation method using an amide-functionalized 1-naphthoate platform as a latent glycosyl leaving group. The amide group facilitates the S(N)2 process by directing the attack of the glycosyl acceptor via H-bonding interaction, resulting in stereoinversion at the anomeric center. Additionally, the amide group enables a safeguarding mechanism by trapping oxocarbenium intermediates, minimizing stereorandom S(N)1 processes. This strategy allows for high-yielding synthesis of a wide range of glycosides with stereoinversion, including challenging 1,2-cis-linkage-rich oligosaccharides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Plant Sciences
Richard Strasser, Georg Seifert, Monika S. Doblin, Kim L. Johnson, Colin Ruprecht, Fabian Pfrengle, Antony Bacic, Jose M. Estevez
Summary: Glycosylation is a crucial modification process that can alter the biological function of proteins and lipids, affecting the development and physiology of an organism. While challenges remain in understanding plant glycosylation, high throughput approaches may help to address these gaps, revolutionizing the identification and characterization of unknown plant glycosyltransferases and hydrolases.
FRONTIERS IN PLANT SCIENCE
(2021)
Article
Chemistry, Organic
Nicholas W. See, Xiaowen Xu, Vito Ferro
Summary: A safe and operationally simple method for the preparation of fi-D-glycosyl fluorides has been presented, demonstrating the facile, high-yielding, and diastereoselective conversions of 2-O-acyl thioglycosides to fi-D- and other 1,2-trans glycosyl fluorides through a precise combination of XtalFluor-M, N-bromosuccinimide, and Et3N·3HF. The roles of these reagents and their interplay on fluorination stereoselectivity are dissected in this study.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kevin Muru, Charles Gauthier
Summary: This article discusses the application of glycosylation and protecting group strategies in synthesizing bioactive glycans, specifically naturally occurring lupane-type saponins and oligosaccharides related to Burkholderia species.
Review
Chemistry, Multidisciplinary
Frank Hollmann, Diederik J. Opperman, Caroline E. Paul
Summary: This review highlights the synthetic state-of-the-art and potential of enzymes catalyzing reductions, ranging from carbonyl, enone, and aromatic reductions to reductive aminations. Enzymes play a key role in producing chiral products with new functionalities, leading to alternative synthetic routes for high-added-value compounds and bulk chemicals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Biotechnology & Applied Microbiology
Caroline E. Paul, Daniel Eggerichs, Adrie H. Westphal, Dirk Tischler, Willem J. H. van Berkel
Summary: Flavoprotein monooxygenases (FPMOs) have evolved from model enzymes in mechanistic flavoprotein research to biotechnologically relevant catalysts for sustainable production of valuable chemicals. FPMOs are classified based on protein structural properties and electron donor specificities, with each group catalyzing different types of oxygenation reactions. Engineering strategies have been utilized to enhance the robustness and applicability of FPMOs.
BIOTECHNOLOGY ADVANCES
(2021)
Article
Chemistry, Multidisciplinary
Shiny Joseph Srinivasan, Sarah E. Cleary, Miguel A. Ramirez, Holly A. Reeve, Caroline E. Paul, Kylie A. Vincent
Summary: A new activity of the [NiFe] uptake hydrogenase 1 in Escherichia coli (Hyd1) was discovered, allowing direct reduction of the biological flavin cofactors FMN and FAD. The robust nature of Hyd1 was utilized for flavin reduction across a range of temperatures and reaction times, demonstrating potential for regenerating FMNH2 or FADH(2) and supporting asymmetric alkene reductions. High turnover frequencies and total turnover numbers were achieved during flavin recycling, showing the efficiency of this system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Xiaomin Xu, Hugo Brasselet, Ewald P. J. Jongkind, Miguel Alcalde, Caroline E. Paul, Frank Hollmann
Summary: In this study, a new enzymatic reaction was developed to produce enantioenriched phenylethanols. By using a two-step cascade reaction, eleven ethylbenzene derivatives were converted into chiral alcohols with high enantioselectivity.
Article
Chemistry, Physical
Ewald P. J. Jongkind, Aurelie Fossey-Jouenne, Ombeline Mayol, Anne Zaparucha, Carine Vergne-Vaxelaire, Caroline E. Paul
Summary: Accessing chiral amines with high enantiomeric and diastereomeric excess was achieved through the development of a bi-enzymatic cascade using Old Yellow Enzyme family enzymes. Different unsaturated carbonyl substrates were successfully converted with up to 99% selectivity, showcasing the potential of this approach for diverse alkene substrates.
Review
Chemistry, Multidisciplinary
Ulf Hanefeld, Frank Hollmann, Caroline E. Paul
Summary: Biocatalysis has had a significant impact on chemical synthesis, influencing the development of organic chemistry. Currently, hydrolases are widely used on an industrial scale, and other enzyme classes are gaining attention for solving synthetic challenges in organic chemistry. The combined efforts of various fields will establish a new toolbox for chemistry. Recent developments in this area are being critically reviewed.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Physical
David Ribeaucourt, Georg T. Hofler, Mehdi Yemloul, Bastien Bissaro, Fanny Lambert, Jean-Guy Berrin, Mickael Lafond, Caroline E. Paul
Summary: This study established a one-pot bienzymatic cascade to synthesize (R)-citronellal and (S)-citronellal, providing important intermediates for the synthesis of (-)-menthol, a highly demanded flavor worldwide.
Article
Biochemistry & Molecular Biology
Robert Rollig, Caroline E. Paul, Katia Duquesne, Selin Kara, Veronique Alphand
Summary: Temperature has a significant impact on enzymatically catalysed reactions. This study investigates the temperature effect on the Baeyer-Villiger oxidation and reveals a decreasing enantioselectivity at higher temperatures. Traditional approaches are unsuitable for determining the complexity of the system. The 'Shape Language Modelling' (SLM) is used to quantify this trend.
Article
Multidisciplinary Sciences
Linyue Zhang, Edward King, William B. Black, Christian M. Heckmann, Allison Wolder, Youtian Cui, Francis Nicklen, Justin B. Siegel, Ray Luo, Caroline E. Paul, Han Li
Summary: Noncanonical redox cofactors are attractive alternatives to NAD(P)(+) in biotransformation, but engineering enzymes to utilize them is challenging. This study presents a high-throughput directed evolution platform that couples cell growth to the cycling of a noncanonical cofactor, NMN+.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiaomin Xu, Jacob M. A. van Hengst, Yejia Mao, Mireia Martinez, Sergi Roda, Martin Floor, Victor Guallar, Caroline E. Paul, Miguel Alcalde, Frank Hollmann
Summary: A peroxygenase-catalysed hydroxylation of organosilanes has been reported, demonstrating efficient conversion of various silane starting materials and high catalyst performance. Molecular modelling of the enzyme-substrate interaction provides a basis for understanding the selectivity of AaeUPO.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yinqi Wu, Caroline E. Paul, Thomas Hilberath, Ewald P. J. Jongkind, Wuyuan Zhang, Miguel Alcalde, Frank Hollmann
Summary: The utilization of fatty acids can be expanded by adding new functionalities to the hydrocarbon part. In this study, a peroxygenase mutant AaeUPO-Fett is demonstrated to selectively oxyfunctionalize fatty acids, leading to the production of ?-1 hydroxy fatty acid (esters). These hydroxy fatty acid (esters) can be further transformed into lactones, alcohols, esters, and amines through multi-enzyme cascades, providing new pathways for fatty acid valorisation.
Review
Chemistry, Physical
Veronique Alphand, Willem J. H. van Berkel, Valentina Jurkas, Selin Kara, Robert Kourist, Wolfgang Kroutil, Francesco Mascia, Marc M. Nowaczyk, Caroline E. Paul, Sandy Schmidt, Jelena Spasic, Paula Tamagnini, Christoph K. Winkler
Summary: The recent increase of interest in photocatalysis has expanded to biocatalysis and led to a surge in the development of light-dependent enzyme-mediated or enzyme-coupled processes. Reviewing the progress in photobiocatalysis, we suggest categorizing it into different disciplines and providing guidelines for reporting research results and performing photobiocatalytic reactions. Overall, we believe that this field enhances the diversity of biocatalytic reactions and harnesses the selectivity of enzymes in photocatalysis. We anticipate that the ongoing enthusiasm for light-dependent enzymatic processes will uncover new photobiocatalytic mechanisms, complementing biocatalysis with novel bond-forming reactions and innovative strategies for utilizing light as a sustainable energy source.
Article
Chemistry, Multidisciplinary
Christian M. M. Heckmann, Caroline E. E. Paul
Summary: Chiral N-heterocycles are commonly found in active pharmaceutical ingredients, but their synthesis often involves the use of heavy metals. Biocatalytic approaches using transaminases have been developed for the asymmetric synthesis of 2-substituted pyrrolidines and piperidines from commercially available ω-chloroketones. This study achieved analytical yields of up to 90% and enantiomeric excesses of >99.5% for each enantiomer, even with bulky substituents. The biocatalytic approach was successfully applied on a 300 mg scale, yielding 84% isolated yield of (R)-2-(p-chlorophenyl)pyrrolidine with >99.5% ee.
Article
Chemistry, Physical
Rocio Villa, Claudia Ferrer-Carbonell, Caroline E. E. Paul
Summary: This study demonstrates the stability of immobilized ene reductase on Celite for the reduction of activated alkenes in micro-aqueous organic solvent. Full conversion was achieved in methyl t-butyl ether, without hydrolysis and racemisation of products. The immobilized ene reductase showed reusability and scalability.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Holly A. Reeve, Jake Nicholson, Farieha Altaf, Thomas H. Lonsdale, Janina Preissler, Lars Lauterbach, Oliver Lenz, Silke Leimkuehler, Frank Hollmann, Caroline E. Paul, Kylie A. Vincent
Summary: We present a recycling system utilizing a soluble hydrogenase for synthetic nicotinamide cofactor analogues. With the coupling of an ene reductase, we achieved quantitative conversion of N-ethylmaleimide to N-ethylsuccinimide. The biocatalyst system retained over 50% activity after 7 hours.
CHEMICAL COMMUNICATIONS
(2022)
