New azodyrecins identified by a genome mining-directed reactivity-based screening

• Atina Rizkiya Choirunnisa,
• Kuga Arima,
• Yo Abe,
• Noritaka Kagaya,
• Kei Kudo,
• Hikaru Suenaga,
• Junko Hashimoto,
• Manabu Fujie,
• Noriyuki Satoh,
• Kazuo Shin-ya,
• Kenichi Matsuda and
• Toshiyuki Wakimoto

Beilstein J. Org. Chem. 2022, 18, 1017–1025, doi:10.3762/bjoc.18.102

• sequence similarity network (SSN) generated by all-vs-all blastp with E-value at 1 × 10−70 classified these “VlmAs'' into more than fourteen groups (Figure 5). In this network, the two Ady7s from Streptomyces sp. RM72 and Streptomyces sp. A1C6 belong to group 3, while VlmA and SRO_1850 belong to groups 12

• –G (7–10) (b). Key correlations in 2D NMR are shown. In vitro characterization of Ady1. Extracted ion chromatograms at m/z 329.3 (black) and m/z 343.3 (blue), corresponding to compound 11 and 8, respectively, are shown. Sequence similarity network of VlmA-like enzymes in the actinobacterial genomes

First series of N-alkylamino peptoid homooligomers: solution phase synthesis and conformational investigation

• Maxime Pypec,
• Laurent Jouffret,
• Claude Taillefumier and
• Olivier Roy

Beilstein J. Org. Chem. 2022, 18, 845–854, doi:10.3762/bjoc.18.85

• second group of molecules (conformation B). In the crystal lattice, each molecule establishes four intermolecular CO···HN hydrogen bonds. Only the inter-residue carbonyl (oxygen atom labeled O2, Figure 3C) participates in this network, making two hydrogen bonds with two different molecules and different

• ); (C) overview of the hydrogen bonding network (conformation A depicted in blue, conformation B in orange), hydrogen bonds (light blue dashed lines), hanging hydrogen bonds (light green dashed lines). NOE effect interaction observed in the 2D-NOESY spectra of monomer 1 and dimer 2 in DMSO-d6

Identification of the new prenyltransferase Ubi-297 from marine bacteria and elucidation of its substrate specificity

• Jamshid Amiri Moghaddam,
• Huijuan Guo,
• Karsten Willing,
• Thomas Wichard and
• Christine Beemelmanns

Beilstein J. Org. Chem. 2022, 18, 722–731, doi:10.3762/bjoc.18.72

• network with Ptases deposited in the Uniprot database (Figure 2 and Table S1 in Supporting Information File 1). A subsequent network analysis uncovered that the genomes of analyzed bacterial genera encoded only four (G1–G4) out of eight previously reported Ptase groups. The first group of Ptases (G1

• gene sequences are deposited at GenBank with the accession numbers ON075815 and ON075816, respectively. Accession number or ID of all other sequences used to infer the pairwise similarity network and phylogenetic tree are provided in Supporting Information File 1, Table S1. Bacterial strains, plasmids

Structural basis for endoperoxide-forming oxygenases

• Takahiro Mori and
• Ikuro Abe

Beilstein J. Org. Chem. 2022, 18, 707–721, doi:10.3762/bjoc.18.71

• the substrate. The substrate asnovolin A binds in the closed conformation through a hydrogen bond network with active site residues (Figure 4D). In this binding mode, C7' of the substrate is 4.2 Å away from the iron center, which is shorter than the distance between the iron center and C13 (6.5 Å

Bioinspired tetraamino-bisthiourea chiral macrocycles in catalyzing decarboxylative Mannich reactions

• Hao Guo,
• Yu-Fei Ao,
• De-Xian Wang and
• Qi-Qiang Wang

Beilstein J. Org. Chem. 2022, 18, 486–496, doi:10.3762/bjoc.18.51

• report a systematic synthesis of tetraamino-bisthiourea chiral macrocycles and their performance in catalyzing the decarboxylative Mannich addition of malonic acid half thioesters (MAHTs) to isatin-derived ketimines. The macrocycle-enabled hydrogen-bonding activation network and the associated confined

A resorcin[4]arene hexameric capsule as a supramolecular catalyst in elimination and isomerization reactions

• Tommaso Lorenzetto,
• Fabrizio Fabris and
• Alessandro Scarso

Beilstein J. Org. Chem. 2022, 18, 337–349, doi:10.3762/bjoc.18.38

• stabilized more effectively by the more symmetric and tighter capsule A (16·8H2O), which is held on by the minimum amount of water to form the network of hydrogen bonds with hydroxy moieties. Indeed, the capsule B, is looser because of the presence of extra water molecules that can arguably interact with

A two-phase bromination process using tetraalkylammonium hydroxide for the practical synthesis of α-bromolactones from lactones

• Yuki Yamamoto,
• Akihiro Tabuchi,
• Kazumi Hosono,
• Takanori Ochi,
• Kento Yamazaki,
• Shintaro Kodama,
• Akihiro Nomoto and
• Akiya Ogawa

Beilstein J. Org. Chem. 2021, 17, 2906–2914, doi:10.3762/bjoc.17.198

• suggestion and experimental support. Funding This research was supported by JSPS KAKENHI (B, 19H02791) and (B, 19H02756), from the Ministry of Education, Culture, Sports, Science and Technology, Japan, and by Kyoto-Advanced Nanotechnology Network.

Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds

• Alemayehu Gashaw Woldegiorgis and
• Xufeng Lin

Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185

• asymmetric bromination reaction afforded monobrominated biaryls with excellent enantioselectivities up to 99% ee (Scheme 4). The experimental and computational studies showed that the highly organized hydrogen-bonding network between a substrate, a chiral phosphoric acid catalyst (CPA 3), and a brominating

Cryogels: recent applications in 3D-bioprinting, injectable cryogels, drug delivery, and wound healing

• Luke O. Jones,
• Leah Williams,
• Tasmin Boam,
• Martin Kalmet,
• Chidubem Oguike and
• Fiona L. Hatton

Beilstein J. Org. Chem. 2021, 17, 2553–2569, doi:10.3762/bjoc.17.171

• ; Introduction Gels can be defined as polymer networks that are expanded throughout their whole volume by a fluid. In the case of hydrogels, the network component is a hydrophilic polymer, and the swelling agent is water [1]. However, their lack of interconnected macropores and elasticity, required properties

• solution is then cooled to below the freezing point of water, whereby ice crystals form. Importantly, here the solvent (water) solidifies (freezes) and forms solid solvent porogens within the structure allowing the polymer network to form around these crystals, templating the porous structure of the final

• cryogel. In chemically crosslinked cryogels (Figure 1a), the monomers polymerise and crosslink (in the presence of a crosslinker) around the ice crystals to form a network. In physically crosslinked cryogels (Figure 1b), once the solution is cooled below the freezing temperature the polymeric precursors

In-depth characterization of self-healing polymers based on π–π interactions

• Josefine Meurer,
• Julian Hniopek,
• Johannes Ahner,
• Michael Schmitt,
• Jürgen Popp,
• Stefan Zechel,
• Kalina Peneva and
• Martin D. Hager

Beilstein J. Org. Chem. 2021, 17, 2496–2504, doi:10.3762/bjoc.17.166

• thermo-analysis (DMTA). The DMTA of P1 and P2 is depicted in Figure 2, revealing a network structure below temperatures of 120 °C. Above this temperature, a sharp transition (within a very small temperature range) and a significant drop of storage and loss modulus could be observed. Accordingly, this

• transition at 125–130 °C, no crossover of G' and G'' could be observed indicating no active supramolecular bonds. Furthermore, at this temperature (80 °C) G' is higher than G'' indicating a network structure of the polymers. This finding correlates with the DSC results, since the π–π interactions are not

• activated and, therefore, the polymer network is intact. Within the transition, the frequency sweeps revealed a crossover of storage and loss modulus showing the activation of the π–π interactions, which goes hand in hand with the DSC results. Thus, a dynamic network structure could be revealed. The

Halides as versatile anions in asymmetric anion-binding organocatalysis

• Lukas Schifferer,
• Martin Stinglhamer,
• Kirandeep Kaur and
• Olga García Macheño

Beilstein J. Org. Chem. 2021, 17, 2270–2286, doi:10.3762/bjoc.17.145

• reported a family of chiral helical tetratriazoles 82 as a new class of anion-binding catalysts, which can be considered as supramolecular anion-binding catalysts (Scheme 18) [22]. Not only is the increased H-bonding network in multidentate 82 beneficial for giving a firm control over both regio- and

An initiator- and catalyst-free hydrogel coating process for 3D printed medical-grade poly(ε-caprolactone)

• Jochen Löblein,
• Thomas Lorson,
• Miriam Komma,
• Tobias Kielholz,
• Maike Windbergs,
• Paul D. Dalton and
• Robert Luxenhofer

Beilstein J. Org. Chem. 2021, 17, 2095–2101, doi:10.3762/bjoc.17.136

• ]. Interestingly, PCL frames made with MEW were used to build up soft network composites [41][42][43] with outstanding mechanical properties, also with weak matrices of interest for tissue engineering applications [44]. Conclusion SIPGP is an interesting complementary technique to modify the surface of MEW printed

Towards new NIR dyes for free radical photopolymerization processes

• Haifaa Mokbel,
• Guillaume Noirbent,
• Didier Gigmes,
• Frédéric Dumur and
• Jacques Lalevée

Beilstein J. Org. Chem. 2021, 17, 2067–2076, doi:10.3762/bjoc.17.133

• filled samples can be potentially used for composite materials and/or adhesives. Both photochemical and photothermal NIR approaches were proposed to initiate polymerization, e.g., for free-radical processes, interpenetrating polymer network (IPN) synthesis, or photopolyaddition reactions [3][4][6][7][8

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

• suggested that XGs are not essential for the creation of the cellulose network [96]. The complexity and diversity of XGs hinder isolation from natural sources and complicates their description. A significant effort was put towards the development of enzymes for selective introduction of the side chains [97

A systems-based framework to computationally describe putative transcription factors and signaling pathways regulating glycan biosynthesis

• Theodore Groth,
• Rudiyanto Gunawan and
• Sriram Neelamegham

Beilstein J. Org. Chem. 2021, 17, 1712–1724, doi:10.3762/bjoc.17.119

• Cytoscape as a network. These data were filtered based on RP and ρ thresholds defined previously. A binding potential (BP) score was computed by taking the product of RP and ρ for each TF–glycogene relationship. TF–glycogene relationships for each cancer type were separated into subnetworks. The Prefuse

Electron-rich triarylphosphines as nucleophilic catalysts for oxa-Michael reactions

• Susanne M. Fischer,
• Simon Renner,
• A. Daniel Boese and
• Christian Slugovc

Beilstein J. Org. Chem. 2021, 17, 1689–1697, doi:10.3762/bjoc.17.117

• acceptors, Michael donors and catalysts used in this study; pKa (respectively pKa of the conjugated acid in case of phosphines) calculated using the pKa prediction platform (neural network result for solvent H2O) available at pka.luo-group.com [20]; below: Conversion of the oxa-Michael reaction of

Photoinduced post-modification of graphitic carbon nitride-embedded hydrogels: synthesis of 'hydrophobic hydrogels' and pore substructuring

• Cansu Esen and
• Baris Kumru

Beilstein J. Org. Chem. 2021, 17, 1323–1334, doi:10.3762/bjoc.17.92

• . Post-modifications of hydrogels propose an attractive platform so that a variety of fresh functions, which are not arising from initial monomers, could be accessible on a parental network. Photoinduced post-modification of hydrogels by embedding semiconductor nanosheets would be of high interest and

• novelty. Here, a metal-free semiconductor graphitic carbon nitride (g-CN)-embedded hydrogel as an initial network was synthesized via redox-couple initiation under dark conditions. Post-photomodification of so-formed hydrogel, thanks to the photoactivity of the embedded g-CN nanosheets, was exemplified in

• two scenarios. The synthesis of ‘hydrophobic hydrogel’ is reported and its application in delayed cation delivery was investigated. Furthermore, pores of the initial hydrogel were modified by the formation of a secondary polymer network. Such a facile and straightforward synthetic protocol to

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

• reagent incorporation into a mixture of monomers which are co-polymerised to create a network of micro- and mesoporous channels that fill the entirety of the tube/column. In a coated wall reactor, the reagent is immobilised onto the inner surface of the reactor. Finally, packed bed reactor columns are

• ). Packed-bed reactors have also been exploited to facilitate enantioselective nitroaldol processes. In 2013, Shibasaki and Kumagai made use of an entangling network of multiwalled carbon nanotubes (MWNT) to trap a Nd/Na bimetallic catalyst, which was shown to be an efficient combination for nitroaldol

Structural effects of meso-halogenation on porphyrins

• Keith J. Flanagan,
• Maximilian Paradiz Dominguez,
• Zoi Melissari,
• Hans-Georg Eckhardt,
• René M. Williams,
• Dáire Gibbons,
• Caroline Prior,
• Gemma M. Locke,
• Alina Meindl,
• Aoife A. Ryan and
• Mathias O. Senge

Beilstein J. Org. Chem. 2021, 17, 1149–1170, doi:10.3762/bjoc.17.88

• porphyrin together extending the network to be an alkyl···porphyrin···alkyl···porphyrin type system. In the next three compounds 13, 13A, and 14 the main structure only differs by the steric demand due to one meso aryl unit (3,4,5- trimethoxyphenyl (13 and 13A), 2,4,6-trimethoxyphenyl (14)) on one side [24

• forms a repeating pattern of face-to-edge interactions with only minimal interference from the axial ligand (Supporting Information File 1, Figure S39A) and a hydrogen-bonded network between the methoxy moieties (Supporting Information File 1, Figure S39B). Both features are expressed throughout the

• arrangement with a 3.704(4) Å separation (Figure 20A) whilst a lateral alignment where the bromine atoms are pointing towards the tolyl groups in a linear network is observed (Figure 20B). The two other motifs seen are the bromine pyrrole interactions which is reciprocated in a head-to-head alignment (Figure

Nitroalkene reduction in deep eutectic solvents promoted by BH₃NH₃

• Chiara Faverio,
• Monica Fiorenza Boselli,
• Patricia Camarero Gonzalez,
• Alessandra Puglisi and
• Maurizio Benaglia

Beilstein J. Org. Chem. 2021, 17, 1041–1047, doi:10.3762/bjoc.17.83

• -EID project Marie Skłodowska-Curie Actions Innovative Training Network–TECHNOTRAIN H2020-MSCA-ITN-2018 Grant Agreement 812944. http://www.technotrain-ITN.eu.

Highly regio- and stereoselective phosphinylphosphination of terminal alkynes with tetraphenyldiphosphine monoxide under radical conditions

• Dat Phuc Tran,
• Yuki Sato,
• Yuki Yamamoto,
• Shin-ichi Kawaguchi,
• Shintaro Kodama,
• Akihiro Nomoto and
• Akiya Ogawa

Beilstein J. Org. Chem. 2021, 17, 866–872, doi:10.3762/bjoc.17.72

• Nanotechnology Network.

Simulating the enzymes of ganglioside biosynthesis with Glycologue

• Andrew G. McDonald and
• Gavin P. Davey

Beilstein J. Org. Chem. 2021, 17, 739–748, doi:10.3762/bjoc.17.64

• those of the central nervous system, where they function in intercellular recognition and communication. We describe an in silico method for determining the metabolic pathways leading to the most common gangliosides, based on the known enzymes of their biosynthesis. A network of 41 glycolipids is

• ganglioside biosynthesis, and altered ganglioside status in cancer, and the effects on network structure are predicted. The simulator is available at the Glycologue website, https://glycologue.org/. Keywords: gangliosides; Glycologue; glycosyltransferases; neuropathy; Svennerholm nomenclature; Introduction

• ], this alternative activity of the enzyme has been included in the model (Table 2). After 11 iterations of the method, the simulator produces 41 unique structures shown in Figure 3, in 49 reactions, with the network shown in Figure 4. Networks and knockouts The structures shown in Figure 3 are divided

Amino- and polyaminophthalazin-1(2H)-ones: synthesis, coordination properties, and biological activity

• Zbigniew Malinowski,
• Emilia Fornal,
• Agata Sumara,
• Renata Kontek,
• Karol Bukowski,
• Beata Pasternak,
• Dariusz Sroczyński,
• Joachim Kusz,
• Magdalena Małecka and
• Monika Nowak

Beilstein J. Org. Chem. 2021, 17, 558–568, doi:10.3762/bjoc.17.50

• angles equal to 27.61 and 28.71°, respectively, and moreover, the methyl groups of the methoxy substituents are directed opposite and towards to the pyridin-2-yl substituents, respectively. The crystal structure of complex 17 is stabilized with a 3D intermolecular hydrogen bond network (Figure S1a

CF₃-substituted carbocations: underexploited intermediates with great potential in modern synthetic chemistry

• Anthony J. Fernandes,
• Armen Panossian,
• Bastien Michelet,
• Agnès Martin-Mingot,
• Frédéric R. Leroux and
• Sébastien Thibaudeau

Beilstein J. Org. Chem. 2021, 17, 343–378, doi:10.3762/bjoc.17.32

Multiswitchable photoacid–hydroxyflavylium–polyelectrolyte nano-assemblies

• Alexander Zika and
• Franziska Gröhn

Beilstein J. Org. Chem. 2021, 17, 166–185, doi:10.3762/bjoc.17.17

• building blocks for the ternary electrostatic self-assembly, forming well-defined supramolecular assemblies with tunable sizes of 50 to 500 nm. Due to the network of possible chemical reactions for the anthocyanidin and the excited-state dissociation of the photoacid upon irradiation, different ways to

• , systems which respond to more than one external trigger have become of great interest [68][69][70][71][72][73]. Hydroxyflavylium cations can exhibit a network of different chemical reactions enabling these molecules to perform as a molecular level optical memory [74][75][76][77][78]. The network of

• step when excited by light irradiation. Due to the network of possible reactions of Flavy, self-assembly can be accessed and triggered in a number of ways. While this study focused on the first proof of concept and the relation of molecular and nanoscale switching, a deeper understanding of the