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

Metal-free nucleophilic trifluoromethylselenolation via an iodide-mediated umpolung reactivity of trifluoromethylselenotoluenesulfonate

• Kevin Grollier,
• Alexis Taponard,
• Arnaud De Zordo-Banliat,
• Emmanuel Magnier and
• Thierry Billard

Beilstein J. Org. Chem. 2020, 16, 3032–3037, doi:10.3762/bjoc.16.252

• grateful to the CNRS and the French Ministry of Research for financial support. The French Fluorine Network is also acknowledged for its support.

Controlled decomposition of SF₆ by electrochemical reduction

• Sébastien Bouvet,
• Bruce Pégot,
• Stéphane Sengmany,
• Erwan Le Gall,
• Eric Léonel,
• Anne-Marie Goncalves and
• Emmanuel Magnier

Beilstein J. Org. Chem. 2020, 16, 2948–2953, doi:10.3762/bjoc.16.244

• potential of −2.3 V/SRE; (left). 19F NMR expansion of the final mixture. Funding S.B. thanks the French Ministry of Research for a Ph.D. grant. The Rhodia-Solvay company is gratefully acknowledged for the gift of sulfur hexafluoride. The French Fluorine Network (GIS Fluor) is acknowledged for financial

Using multiple self-sorting for switching functions in discrete multicomponent systems

• Amit Ghosh and
• Michael Schmittel

Beilstein J. Org. Chem. 2020, 16, 2831–2853, doi:10.3762/bjoc.16.233

• reactions in a double self-sorting protocol [60]. The operation of the network required the addition and removal of zinc(II) ions which triggered three distinct events in parallel: i) a mutually dependent self-sorting of different nanorotors and reshuffling of the components, ii) a switching between vastly

Dirhamnolipid ester – formation of reverse wormlike micelles in a binary (primerless) system

• David Liese,
• Hans Henning Wenk,
• Xin Lu,
• Jochen Kleinen and
• Gebhard Haberhauer

Beilstein J. Org. Chem. 2020, 16, 2820–2830, doi:10.3762/bjoc.16.232

• is typical for wormlike micelle systems, the normalized Cole–Cole plot of G''/G''max against G'/G''max was obtained as a semicircle centered at G'/G''max = 1. The formation of network structures was also verified by polarized light microscopy. The sample was birefringent at ambient temperature and

• polarity. An unusual behavior was observed when the dirhamnolipid esters were added to toluene. The more polar short chain length dirhamnolipid esters and 7 form a gel-like texture in toluene, indicating the formation of a network structure of the surfactant molecules. With increasing chain length of the

• can be explained with an inhomogeneous breakup of the three-dimensional structure. In the beginning, the network collapses into big chunks, while the surrounding material is still rigid. A further increase in the temperature leads to a dominating viscous behavior until the whole sample becomes fluid

Optical detection of di- and triphosphate anions with mixed monolayer-protected gold nanoparticles containing zinc(II)–dipicolylamine complexes

• Lena Reinke,
• Julia Bartl,
• Marcus Koch and
• Stefan Kubik

Beilstein J. Org. Chem. 2020, 16, 2687–2700, doi:10.3762/bjoc.16.219

• longer wavelength. A network of a lighter material also appeared in these images, which could indicate the presence of insoluble zinc(II) diphosphate (Figure 7b). The TEM images of a solution of NP(R)-1 to which Zn(NO3)2 and sodium diphosphate were sequentially added indeed featured similar structures

A consensus-based and readable extension of Linear Code for Reaction Rules (LiCoRR)

• Benjamin P. Kellman,
• Yujie Zhang,
• Emma Logomasini,
• Eric Meinhardt,
• Karla P. Godinez-Macias,
• Austin W. T. Chiang,
• James T. Sorrentino,
• Chenguang Liang,
• Bokan Bao,
• Yusen Zhou,
• Sachiko Akase,
• Isami Sogabe,
• Thukaa Kouka,
• Elizabeth A. Winzeler,
• Iain B. H. Wilson,
• Matthew P. Campbell,
• Sriram Neelamegham,
• Frederick J. Krambeck,
• Kiyoko F. Aoki-Kinoshita and
• Nathan E. Lewis

Beilstein J. Org. Chem. 2020, 16, 2645–2662, doi:10.3762/bjoc.16.215

• α-2,6-linked sialic acid (NNa6) whose linkage position is unknown. Here, the “ | ” is used to separate the fragment(s) and core structure components (UR6). In the interest of demonstrating the reach of single letter LC monosaccharides (Table 4), we provide a monosaccharide network suggesting

• monosaccharide listed by SNFG (Figure 2D). Figure 2D shows some of these non-trivial paths (e.g., beyond GlcNac; G → GN or G[2N]) from Table 4 monosaccharides, to all listed SFNG monosaccharides via modifications from Table 5. We further provide a full network (Table S6, Supporting Information File 1) to

• Rules Linear Code was first used to represent reaction rules in 2009. A reaction network, specifying glycans with condensed IUPAC and Linear Code, was trained on mass spectrometry abundance to learn biosynthetic enzyme activities [10]. Their reaction rules table contained four features: enzyme, reactant

NMR Spectroscopy of supramolecular chemistry on protein surfaces

• Peter Bayer,
• Anja Matena and
• Christine Beuck

Beilstein J. Org. Chem. 2020, 16, 2505–2522, doi:10.3762/bjoc.16.203

Dawn of a new era in industrial photochemistry: the scale-up of micro- and mesostructured photoreactors

• Emine Kayahan,
• Mathias Jacobs,
• Leen Braeken,
• Leen C.J. Thomassen,
• Simon Kuhn,
• Tom van Gerven and
• M. Enis Leblebici

Beilstein J. Org. Chem. 2020, 16, 2484–2504, doi:10.3762/bjoc.16.202

• NETmix reactor with a monolithic reactor packed with translucent cellulose acetate monolithic structures. The front glass of the slab, the network of the channels, and the chambers imprinted in the back stainless steel slab of the NETmix reactor were coated with a thin-film photocatalyst (TiO2-P25) by

Computational tools for drawing, building and displaying carbohydrates: a visual guide

• Kanhaya Lal,
• Rafael Bermeo and
• Serge Perez

Beilstein J. Org. Chem. 2020, 16, 2448–2468, doi:10.3762/bjoc.16.199

A proposed sustainability index for synthesis plans based on input provenance and output fate: application to academic and industrial synthesis plans for vanillin as a case study

• John Andraos

Beilstein J. Org. Chem. 2020, 16, 2346–2362, doi:10.3762/bjoc.16.196

• Sustainability of vanillin plans The exercise of partitioning input materials according to their provenance and output materials according to their fate is extremely challenging because it requires a completely transparent knowledge and access to the entire network supply and end-of-life chains that constitute

• complete macroscopic knowledge and connectivity of all elements pertaining to the network of all chemical processes involved in a given synthesis plan. At this time reliable estimates of these rates are not readily available to the average practicing chemist or chemical engineer in established open-access

Photosensitized direct C–H fluorination and trifluoromethylation in organic synthesis

• Shahboz Yakubov and
• Joshua P. Barham

Beilstein J. Org. Chem. 2020, 16, 2151–2192, doi:10.3762/bjoc.16.183

How and why plants and human N-glycans are different: Insight from molecular dynamics into the “glycoblocks” architecture of complex carbohydrates

• Carl A. Fogarty,
• Aoife M. Harbison,
• Amy R. Dugdale and
• Elisa Fadda

Beilstein J. Org. Chem. 2020, 16, 2046–2056, doi:10.3762/bjoc.16.171

• synergistic effect as this conformation is stabilized by a hydrogen bonding network involving the core fucose, the GlcNAc on the (1-6) arm and the xylose, as shown in Figure S1, Supporting Information File 1. Such folding event has been observed as a stable conformation in two independent simulations. To note

• (open) conformation, while the closed conformation, which accounts for the remaining 10% is achieved through a rotation around the core Man-β(1-4)-GlcNAc. The lack of interaction between the arms is due to the inability to establish the same stable hydrogen bonding network due to the non-complementary

• specific branching and spatial orientation of the motif allowed for a stable interaction between the arms, which is not observed in complex N-glycans with a linear functionalization of the arms [24]. Notably, the same hydrogen bonding network between the arms cannot be established when the same N-glycan

Automated high-content imaging for cellular uptake, from the Schmuck cation to the latest cyclic oligochalcogenides

• Rémi Martinent,
• Javier López-Andarias,
• Dimitri Moreau,
• Yangyang Cheng,
• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2020, 16, 2007–2016, doi:10.3762/bjoc.16.167

• stable HGM cells with HaloTag–GFP on mitochondria, labeled with 26, showing the fluorescence intensity of GFP versus 26 in a) selected cells inside the cell body mask (light blue and yellow areas in Figure 7a) and in b) selected regions with a high GFP signal, considered as the mitochondrial network

Polarity effects in 4-fluoro- and 4-(trifluoromethyl)prolines

• Vladimir Kubyshkin

Beilstein J. Org. Chem. 2020, 16, 1837–1852, doi:10.3762/bjoc.16.151

• analogues with distinct hydrophobic properties can impact their ability to pass biomembranes [54][55][56]. A crystallographic study has shown that when included into a protein structure, a fluorine atom exhibits a network of interaction within a protein core [57]. Another recent study showed that the

• . Nonetheless, it is barely conclusive to approach interaction of complex molecules with solvents using net dipole alone. For example, even for the relatively simple molecules like 1–4, the net dipole would not adequately represent neither the complexity of the interaction network within the molecule, nor

One-pot synthesis of isosorbide from cellulose or lignocellulosic biomass: a challenge?

• Isaline Bonnin,
• Raphaël Mereau,
• Thierry Tassaing and
• Karine De Oliveira Vigier

Beilstein J. Org. Chem. 2020, 16, 1713–1721, doi:10.3762/bjoc.16.143

• ; isosorbide; lignocellulosic biomass; Introduction Cellulose, a homopolymer of ᴅ-glucose, is the most abundant component of lignocellulosic biomass. Cellulose is a crystalline polymer due to its intra- and intermolecular hydrogen bond network. The conversion of cellulose to added value chemicals has received

Models of necessity

• Timothy Clark and
• Martin G. Hicks

Beilstein J. Org. Chem. 2020, 16, 1649–1661, doi:10.3762/bjoc.16.137

• computational studies. Furthermore, reactions often follow competing paths, where the dominance of one over another often depends on the specific reaction conditions and only minor variations can give rise to a different outcome. Biological systems have a network of pathways and it is often very difficult to

Mechanochemical green synthesis of hyper-crosslinked cyclodextrin polymers

• Alberto Rubin Pedrazzo,
• Fabrizio Caldera,
• Marco Zanetti,
• Silvia Lucia Appleton,
• Nilesh Kumar Dhakar and
• Francesco Trotta

Beilstein J. Org. Chem. 2020, 16, 1554–1563, doi:10.3762/bjoc.16.127

• . Polysaccharides and, among them, starch derivatives such as cyclodextrins (CD), have recently emerged as they are safe, of low cost and biodegradable. Cyclodextrin nanosponges (CD-NS) are crosslinked cyclodextrin polymers characterized by a nanosized three-dimensional network. The reactive hydroxy groups of CDs

• allow them to act as polyfunctional monomers, permitting the crosslinking with bi- or multifunctional chemicals, such as dianhydrides, diisocyanates, diepoxides, and dicarboxylic acids, etc. The polarity and size of the polymer network can be easily tuned by varying the type of the crosslinker and

• in the tested solvents, in accordance with the formation of a crosslinked network and with data from previous literature [9]. Figure 1 reports FTIR spectra of the cyclodextrin NS, with a comparison between βNS-CDI 1:4 obtained through ball-mill synthesis and βNS-CDI 1:4 from synthesis in DMF and a

Heterogeneous photocatalysis in flow chemical reactors

• Christopher G. Thomson,
• Ai-Lan Lee and
• Filipe Vilela

Beilstein J. Org. Chem. 2020, 16, 1495–1549, doi:10.3762/bjoc.16.125

• polymer chains, charge transport is limited to intraplanar transport along the conjugated network. In crystalline and graphitic organic materials, the close packing of two-dimensional sheets permits interplanar charge transport in the third dimension, allowing the delocalisation of charge over several