Article
Chemistry, Multidisciplinary
Caroline Poock, Markus Kalesse
Summary: The first total synthesis of halioxepine was achieved using 1,4-addition for constructing the quaternary center at C10 and halo etherification for generating the tertiary ether at C7. The correct structure of halioxepine was determined by assembling different enantiomeric building blocks and adjusting the relative configuration between C10 and C15.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Mira Holzheimer, Jaap S. Sinninghe Damste, Stefan Schouten, Remco W. A. Havenith, Ana V. Cunha, Adriaan J. Minnaard
Summary: Crenarchaeol is a glycerol dialkyl glycerol tetraether lipid exclusively produced in Archaea, with a highly complex structure that is considered iconic in organic geochemistry. Researchers have successfully completed the first total synthesis of the proposed structure of crenarchaeol, leading to a revised understanding of its chemical composition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Shoji Kobayashi, Tomoki Tamura, Mizuho Koshishiba, Takeshi Yasumoto, Satoshi Shimizu, Tomoki Kintaka, Kaoru Nagai
Summary: The first total syntheses of hericenones C-H and putative 3-hydroxyhericenone F were achieved, with the structure of the putative compound revised to hericenone Z. Through biological activity studies, it was found that hericenone analogues may have potential neuroprotective effects.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hidetaka Kuroiwa, Soichiro Suzuki, Kazuhiro Irie, Chihiro Tsukano
Summary: Lancilactone C is a tricyclic triterpenoid that can inhibit the replication of human immunodeficiency virus (HIV) in H9 lymphocytes without cytotoxicity. It has a tricyclic skeleton consisting of trans-dimethyl-bicyclo[4.3.0]nonane and 7-isopropylene-cyclohepta-1,3,5-triene. The latter structure, in which all carbon atoms are sp (2) hybridized, is unique and needs to be synthetically verified.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Fangzhi Han, Guangju Liu, Xuhai Zhang, Yahui Ding, Liang Wang, Yijing Wu, Yue Chen, Quan Zhang
Summary: For the first time, the 15-membered cyclic depsipeptide boholamide A and an epimer were prepared by total synthesis, leading to a revision of the C6 stereochemistry in the original proposed structure. The revised boholamide A was synthesized in 16 linear steps with an overall yield of 5.46%, facilitating investigations into its potential as a hypoxia-selective anticancer agent.
Article
Biochemistry & Molecular Biology
Jelena Kesic, Ivana Kovacevic, Mirjana Popsavin, Goran Benedekovic, Marko V. Rodic, Vesna Kojic, Velimir Popsavin
Summary: The development of a synthetic route allowed for the synthesis of cleistanolates and their stereoisomers, leading to the revision and confirmation of their absolute stereochemistry. The synthesis involved key steps such as zinc-mediated THF ring-opening and stereoselective dihydroxylation. The first total synthesis of cleistanolate was achieved starting from D-xylose in just eight steps. The cytotoxicity of the natural product was briefly investigated.
BIOORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Chihiro Uchiyama, Akane Fukuda, Minagi Mukaiyama, Yoshiki Nakazawa, Yuka Kuramochi, Kyohei Muguruma, Mitsue Arimoto, Akihiro Ninomiya, Koichiro Kako, Yohei Katsuyama, Sho Konno, Akihiro Taguchi, Kentaro Takayama, Atsuhiko Taniguchi, Yoko Nagumo, Takeo Usui, Yoshio Hayashi
Summary: The structure of natural cyclic depsipeptide MA026 was revised through physicochemical analysis and total solid-phase synthesis, showing similar biological activity as the natural one. This revised structure has potential implications for the synthesis and application of MA026.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Julian Baars, Isabelle Grimm, Dirk Blunk, Joerg-Martin Neudoerfl, Hans-Guenther Schmalz
Summary: A 12-step total synthesis of the natural product dysiherbol A was achieved, revealing the need for revision of the originally proposed structure and absolute configuration. The synthesis involved key steps including Cu-catalyzed addition/enolate-trapping, Au-catalyzed double cyclization, and late installation of the C5-bridgehead methyl group. Spectroscopic measurements confirmed the identity of the synthetic compound with the natural product but with an opposite molecular rotation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Timm O. Koller, Ullrich Scheid, Teresa Koesel, Jennifer Herrmann, Daniel Krug, Helena I. M. Boshoff, Bertrand Beckert, Joanna C. Evans, Jan Schlemmer, Becky Sloan, Danielle M. Weiner, Laura E. Via, Atica Moosa, Thomas R. Ioerger, Michael Graf, Boris Zinshteyn, Maha Abdelshahid, Fabian Nguyen, Stefan Arenz, Franziska Gille, Maik Siebke, Tim Seedorf, Oliver Plettenburg, Rachel Green, Anna-Luisa Warnke, Joachim Ullrich, Ralf Warrass, Clifton E. Barry, Digby F. Warner, Valerie Mizrahi, Andreas Kirschning, Daniel N. Wilson, Rolf Mueller
Summary: The resistance of bacterial pathogens against antibiotics is a major global health threat according to the WHO. The myxobacterial antibiotic myxovalargin has been found to be highly effective against Mycobacterium tuberculosis. Detailed study of myxovalargin biosynthesis has enabled the production of this compound through fermentation. Functional genomics analysis and feeding experiments have suggested a structural revision, which was confirmed through the development of a concise total synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Koichiro Ota, Kazuo Kamaike, Hiroaki Miyaoka
Summary: The first asymmetric total synthesis of norsesquiterpenoid saniculamoid D was achieved from a previously known pure chiral imide with a longest linear sequence of seven steps. The key feature of the synthesis was the formation of the bicyclo[3.1.0]hexane moiety through Julia-Kocienski olefination and Hodgson cyclopropanation. Notably, the NMR spectra and specific rotation value of the synthesized structure did not match those of the natural compound, leading to the reassignment of the correct structure of saniculamoid D, which now corresponds to the initially proposed structure for chromolaevanedione.
Article
Biochemistry & Molecular Biology
Mikhail Elyashberg, Sriram Tyagarajan, Mihir Mandal, Alexei V. Buevich
Summary: Natural products are important sources of biologically active compounds, but determining their structures accurately can be challenging. This paper proposes using computer-assisted structure elucidation (CASE) and density functional theory (DFT) methods to verify and correct the structures of natural products. The authors demonstrated that in 12 real cases of structure revisions, CASE and DFT could have saved time and resources compared to total synthesis methods. In all cases, the correct structures were determined within minutes using the originally published NMR and MS data, even when the data was incomplete or contained errors.
Article
Chemistry, Organic
Santanu Jana, Vikram A. Sarpe, Suvarn S. Kulkarni
Summary: In this study, a total synthesis strategy for the structurally unique fungal glycolipid fusaroside was reported, with a proposed revision in its structure, particularly regarding the position of olefins in the lipid chain.
Article
Plant Sciences
Masahito Yoshida, Tomoya Matsushita, Shinji Kondo, Hiroko Isoda, Hideo Kigoshi
Summary: The structure of trichomide D has been revised through total synthesis, and the configuration of the chlorohydrin moiety was found to be a pivotal factor for exhibiting potent cytotoxicity against cancer cells.
JOURNAL OF NATURAL PRODUCTS
(2022)
Article
Chemistry, Organic
Balasaheb R. Borade, Ravindar Kontham
Summary: A chiral-pool protecting-group-free five-step total synthesis of tetranorsesquiterpenoide (+)-lanceolactone A and its stereoisomers was achieved using linalool as building blocks. The key steps in this synthesis include regioselective ozonolysis, cycloisomerization-induced construction of furan, and dye-sensitized photo-oxidation. The absolute configuration of natural lanceolactone A was determined using electronic circular dichroism (ECD) and optical rotation data. The study also extended the application of Feringa and Gawronski's CD correlation method.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Dong Guk Nam, Jin Won Lee, Hyun Sil Jung, Do Hyun Ryu
Summary: In this study, optically active (E)-beta-branched Morita-Baylis-Hillman (MBH) esters were prepared using both photochemical and thermal methods. The obtained esters were utilized for the asymmetric synthesis of (E)-Secobutanolide series and (+)-Litseakolide F and G. Revised structures for (+)-Litseakolide F and G were proposed based on these investigations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Microbiology
Lars J. Lindstad, Galiana Lo, Shaun Leivers, Zijia Lu, Leszek Michalak, Gabriel V. Pereira, Asmund K. Rohr, Eric C. Martens, Lauren S. McKee, Petra Louis, Sylvia H. Duncan, Bjorge Westereng, Phillip B. Pope, Sabina Leanti La Rosa
Summary: The study demonstrates that the dominant butyrate producer Faecalibacterium prausnitzii in the human gut is able to acquire and degrade various beta-mannooligosaccharides, contributing to a more comprehensive understanding of beta-mannan metabolism and the cross-feeding interactions between beneficial microbes in the human gut. The findings highlight the importance of microbial metabolism of beta-mannans/beta-MOS as a common dietary component, offering potential insights for developing dietary formulations that may boost this beneficial symbiont and butyrate production in the gut.
Article
Chemistry, Multidisciplinary
Amalie F. Reinertsen, Karoline G. Primdahl, Roberta De Matteis, Jesmond Dalli, Trond V. Hansen
Summary: The study presented the first total synthesis of RvD2(n-3 DPA), a biologically formed mediator derived from omega-3 fatty acid n-3 docosapentaenoic acid. The synthetic lipid mediator exhibited matching physical properties and biological activities with those of naturally produced material, including enhancing macrophage uptake of bacteria and bioparticles.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Fredrik Gjerstad Stopamo, Asmund Kjendseth Rohr, Sophanit Mekasha, Dejan M. Petrovic, Aniko Varnai, Vincent G. H. Eijsink
Summary: The study reports the structural and functional characteristics of a single-domain AA11 LPMO from Aspergillus fumigatus. The LPMO, AfAA11A, shows substrate-binding surface features similar to those of known chitin-active LPMOs and exhibits considerable affinity for both alpha-chitin and beta-chitin, enhancing chitin degradation.
JOURNAL OF BIOLOGICAL CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Gard Gjessing, Lars-Inge Gammelsaeter Johnsen, Simen Gjelseth Antonsen, Jens M. J. Nolsoe, Yngve Stenstrom, Trond Vidar Hansen
Summary: Monohydroxylated polyunsaturated fatty acids are natural compounds found in marine, terrestrial, and human sources. They have attracted significant interest due to their biological activities and role in biosynthetic pathways. This paper presents the preparation of 3-(R)-hydroxyeicosapentaenoic acid and its enantiomer through acetate type aldol reactions.
Article
Dentistry, Oral Surgery & Medicine
Maria G. Balta, Olav Schreurs, Trond V. Hansen, Jorn E. Tungen, Anders Vik, Enrico Glaab, Thomas M. Kuntziger, Karl Schenck, Espen S. Baekkevold, Inger Johanne S. Blix
Summary: This study found that oral epithelial cells express FPR2/ALX and DRV1/GPR32 receptors, and exposure to RvD1(n-3 DPA) induces intracellular calcium mobilization, FPR2/ALX internalization, DRV1/GPR32 translocation, and significantly increases the expression of genes coding for beta-defensin 1, beta-defensin 2, and cathelicidin.
EUROPEAN JOURNAL OF ORAL SCIENCES
(2022)
Article
Biochemistry & Molecular Biology
Sofie S. Kristensen, Thomas F. Oftedal, Asmund K. Rohr, Vincent G. H. Eijsink, Geir Mathiesen, Dzung B. Diep
Summary: This study investigates the molecular mechanisms underlying the interaction between RseP and Enterocin K1 (EntK1) and the bacteriocin sensitivity. Through mutational analysis, the researchers identified key regions and motifs of RseP involved in bacteriocin binding and activity. They found that the extracellular PDZ domain is the main determinant of EntK1 sensitivity. These findings may contribute to the development of novel bacteriocins and the identification of RseP as a potential antibacterial target.
JOURNAL OF BIOLOGICAL CHEMISTRY
(2022)
Article
Orthopedics
Niels Brinkman, Dayal Rajagopalan, David Ring, Gregg Vagner, Lee J. Reichel, Tom Crijns
Summary: This survey-based study found that surgeons who received supportive information could identify more instances of language reflecting unhelpful thoughts or distress regarding symptoms. However, there was limited agreement among surgeons in their ratings of such language, indicating low reliability.
CLINICAL ORTHOPAEDICS AND RELATED RESEARCH
(2023)
Article
Anesthesiology
Kenta Furutani, Ouyang Chen, Aidan McGinnis, Yuqing Wang, Charles N. Serhan, Trond Vidar Hansen, Ru-Rong Ji
Summary: The article demonstrates that 3-oxa-PD1 effectively reduces both acute and chronic itch in mouse models by regulating synaptic transmission and astroglial LCN2 production. Stable SPM analogs like 3-oxa-PD1 could be useful in treating pruritus associated with different skin injuries.
Article
Biochemistry & Molecular Biology
Ole Golten, Ivan Ayuso-Fernandez, Kelsi R. Hall, Anton A. Stepnov, Morten Sorlie, asmund Kjendseth Rohr, Vincent G. H. Eijsink
Summary: The catalytic activity of polysaccharide-degrading mono-copper lytic polysaccharide monooxygenases (LPMOs) is affected by the choice of reductant and pH. The reaction rate with ascorbic acid is not pH-dependent between pH 6.0 and 8.0, while the reaction rate with gallic acid increases at higher pH. This correlation is attributed to the ionization state of the reductant, which affects its ability to generate H2O2 from molecular oxygen. However, l-cysteine shows a different behavior due to increased binding to the copper active site at higher pH, counteracting the increase in H2O2 production.
Article
Plant Sciences
Karina Ervik, Amalie F. Reinertsen, Duco S. Koenis, Jesmond Dalli, Trond V. Hansen
Summary: The methyl ester of resolvin D5(n-3 DPA), a lipid mediator derived from the omega-3 fatty acid n-3 docosapentaenoic acid, was successfully synthesized in a stereoselective manner. The physical properties of the synthetic material were compared to those of materials from human blood and mouse exudates. In biological experiments, the synthetic RvD5(n-3 DPA) displayed potent leukocyte-directed activities.
JOURNAL OF NATURAL PRODUCTS
(2023)
Article
Chemistry, Multidisciplinary
Kelsi R. Hall, Chris Joseph, Ivan Ayuso-Fernandez, Ashish Tamhankar, Lukas Rieder, Rannei Skaali, Ole Golten, Frank Neese, Asmund K. Rohr, Sergio A. V. Jannuzzi, Serena DeBeer, Vincent G. H. Eijsink, Morten Sorlie
Summary: By mutating a conserved glutamine/glutamate in Lytic polysaccharide monooxygenases (LPMOs), it was found that the nature and distance of the headgroup to the copper can fine-tune the functionality and reactivity of LPMOs. The presence of glutamate near the copper decreased the reduction potential and the ratio between reduction and reoxidation rates. These findings provide important insights for understanding LPMOs and LPMO-inspired synthetic catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Asmund Stenvik Haatveit, Trond Vidar Hansen
Summary: This article discusses the biosynthetic pathways and local biochemical metabolism of the specialized pro-resolving mediator (SPM) protectin D1 (PD1), highlighting its potent pro-resolution and anti-inflammatory bioactions. The protectins, together with the lipoxins, resolvins, and maresins, form the four individual SPM families that have garnered significant interest in basic biomedical research and drug discovery efforts.
PROSTAGLANDINS & OTHER LIPID MEDIATORS
(2023)
Meeting Abstract
Biochemistry & Molecular Biology
G. Valerio, A. K. Rohr, J. J. G. Moura, C. Cordas
Meeting Abstract
Biochemistry & Molecular Biology
C. M. Cordas, G. N. Valerio, A. K. Rohr, V. G. H. Eijsink, J. J. G. Moura
Article
Chemistry, Multidisciplinary
Amalie F. Reinertsen, Karoline G. Primdahl, Roberta De Matteis, Jesmond Dalli, Trond V. Hansen
Summary: This study presents the first total synthesis of RvD2(n-3 DPA), a mediators biosynthesized from the omega-3 fatty acid n-3 docosapentaenoic acid, showing potent biological activities and matching physical property data with biologically produced material.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
