Selective synthesis of α-organylthio esters and α-organylthio ketones from β-keto esters and sodium S-organyl sulfurothioates under basic conditions

• Jean C. Kazmierczak,
• Roberta Cargnelutti,
• Thiago Barcellos,
• Claudio C. Silveira and
• Ricardo F. Schumacher

Beilstein J. Org. Chem. 2021, 17, 234–244, doi:10.3762/bjoc.17.24

• reported by the previous literature shown in Scheme 1. As such, intrigued by this result and aiming to find selective methods to prepare both α-thio carbonyl compounds (3a and 4a), we decided to verify the influence of different inorganic and organic bases on the reaction (Table 1, entries 2–9). During

• conditions to obtain ethyl 2-(benzylthio)acetate (3a) selectively and in a high yield in hand (Table 1, entry 22), we turned our attention to find an ideal protocol to synthesize 4a. When 0.5 mmol of 1a and 1 mmol of 2a were used in the presence of 2 equivalents of NaOH under air, compound 4a was obtained in

Tuning the solid-state emission of liquid crystalline nitro-cyanostilbene by halogen bonding

• Subrata Nath,
• Alexander Kappelt,
• Matthias Spengler,
• Bibhisan Roy,
• Jens Voskuhl and
• Michael Giese

Beilstein J. Org. Chem. 2021, 17, 124–131, doi:10.3762/bjoc.17.13

• design of luminescent liquid crystals. In supramolecular liquid crystals, however, it did not find application so far [24]. We also studied the temperature dependence of the fluorescence behaviour. In the solid state at room temperature, NO2-C9∙∙∙F4St shows a high intensity emission at λ = 545 nm, which

Supramolecular polymers with reversed viscosity/temperature profile for application in motor oils

• Jan-Erik Ostwaldt,
• Christoph Hirschhäuser,
• Stefan K. Maier,
• Carsten Schmuck and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2021, 17, 105–114, doi:10.3762/bjoc.17.11

• Figure 6 for compound 2 in toluene, see Supporting Information File 1, chapter 7 for compound 1 and other solvents). Here, an effect of the temperature on the hydrodynamic radius can be observed. We find two different peak areas, one with sizes of 10–40 nm and one with 100–700 nm. At 25 °C, the peak area

Recent progress in the synthesis of homotropane alkaloids adaline, euphococcinine and N-methyleuphococcinine

• Dimas J. P. Lima,
• Antonio E. G. Santana,
• Michael A. Birkett and
• Ricardo S. Porto

Beilstein J. Org. Chem. 2021, 17, 28–41, doi:10.3762/bjoc.17.4

• acids as catalysts for C-allylation of unprotected oximes with allyl boronates [58]. After screening to find the best reaction conditions, oxime 103 was converted to α-tertiary acetal-protected hydroxylamine (±)-104 in the presence of 3,5-difluorophenylboronic acid and diisopropyl allyl boronate (108

Semiautomated glycoproteomics data analysis workflow for maximized glycopeptide identification and reliable quantification

• Steffen Lippold,
• Arnoud H. de Ru,
• Jan Nouta,
• Peter A. van Veelen,
• Magnus Palmblad,
• Manfred Wuhrer and
• Noortje de Haan

Beilstein J. Org. Chem. 2020, 16, 3038–3051, doi:10.3762/bjoc.16.253

• additional modifications), the glycome, and the sample matrix [11]. A recent study by us applied a threshold score of 200 for the IgG/IgA glycopeptides from human serum, aiming to find a balance between the exclusion of false positives while preventing false negatives [17]. Sensitive glycopeptide assignments

Construction of pillar[4]arene[1]quinone–1,10-dibromodecane pseudorotaxanes in solution and in the solid state

• Xinru Sheng,
• Errui Li and
• Feihe Huang

Beilstein J. Org. Chem. 2020, 16, 2954–2959, doi:10.3762/bjoc.16.245

• the hydrogen atoms on the ethoxy groups. It is worth mentioning that we did not find any interaction of the benzoquinone subunit of the host with the guest molecule. Host–guest complexation in solution In order to further study the host–guest binding properties of H and G, we explored the complexation

Regioselective synthesis of heterocyclic N-sulfonyl amidines from heteroaromatic thioamides and sulfonyl azides

• Vladimir Ilkin,
• Vera Berseneva,
• Tetyana Beryozkina,
• Tatiana Glukhareva,
• Lidia Dianova,
• Wim Dehaen,
• Eugenia Seliverstova and
• Vasiliy Bakulev

Beilstein J. Org. Chem. 2020, 16, 2937–2947, doi:10.3762/bjoc.16.243

• sulfonyl azides. Due to the high dipole moment, the presence of electronegative heteroatoms bearing electron lone pairs, one could propose alternative reactions which might make it difficult to find a general regioselective procedure for the synthesis of the target molecules in good yields. To the best of

Synthesis of imidazo[1,5-a]pyridines via cyclocondensation of 2-(aminomethyl)pyridines with electrophilically activated nitroalkanes

• Dmitrii A. Aksenov,
• Nikolai A. Arutiunov,
• Vladimir V. Maliuga,
• Alexander V. Aksenov and
• Michael Rubin

Beilstein J. Org. Chem. 2020, 16, 2903–2910, doi:10.3762/bjoc.16.239

• recently demonstrated, this type of species can be efficiently generated upon the treatment of nitroalkanes with anhydrous H3PO4 or in combination with 87% PPA [44]. We were pleased to find that the performance of the direct transformation of 12 into 16a was significantly improved after doping the PPA

One-pot multicomponent green Hantzsch synthesis of 1,2-dihydropyridine derivatives with antiproliferative activity

• Giovanna Bosica,
• Kaylie Demanuele,
• José M. Padrón and
• Adrián Puerta

Beilstein J. Org. Chem. 2020, 16, 2862–2869, doi:10.3762/bjoc.16.235

• find a green catalyst that could provide a wide substrate scope for the Hantzsch synthesis of 1,2-dihydropyridines in a short reaction time. In order to achieve a green method, apart from utilizing a multicomponent reaction as a route providing a high atom economy, heterogeneous catalysis should be

Changed reactivity of secondary hydroxy groups in C8-modified adenosine – lessons learned from silylation

• Jennifer Frommer and
• Sabine Müller

Beilstein J. Org. Chem. 2020, 16, 2854–2861, doi:10.3762/bjoc.16.234

• as the temperature were varied in order to find conditions for preferred 2’-O-silylation (Table 1). Unfortunately, all tested reaction conditions failed. AgNO3 was found being absolutely essential for the reaction to proceed. In its absence neither the 2’-, nor the 3’-isomer was formed, whereas in

• concluded from NMR analysis, this also applies to the adenosine derivative reported here. However, standard reaction conditions that should preferentially lead to the 2’-O-TBDMS isomer, here favored formation of the 3’-O-isomer in fourfold excess, and we were not able to find conditions that would reverse

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

• -reducing) end of another. The key property of a ligand substring is that all the included branches of the ligand are completely contained in the substring. Continuation “_” – As we parse from left to right through a substring, we may find left parenthesis (entering into a branch) and right parenthesis

Synthesis and characterization of S,N-heterotetracenes

• Astrid Vogt,
• Florian Henne,
• Christoph Wetzel,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2020, 16, 2636–2644, doi:10.3762/bjoc.16.214

• systems. The various obtained heteroatom sequences ‘SSNS’ (SN4), ‘SNNS’ (SN4’’), and ‘NSSN’ (SN4’) allowed for evaluation of structure–property relationships relative to the sulfur analogue tetrathienoacene (‘SSSS’). In line with the results for the whole series of S,N-heteroacenes, we find that

Anion exchange resins in phosphate form as versatile carriers for the reactions catalyzed by nucleoside phosphorylases

• Julia N. Artsemyeva,
• Ekaterina A. Remeeva,
• Tatiana N. Buravskaya,
• Irina D. Konstantinova,
• Roman S. Esipov,
• Anatoly I. Miroshnikov,
• Natalia M. Litvinko and
• Igor A. Mikhailopulo

Beilstein J. Org. Chem. 2020, 16, 2607–2622, doi:10.3762/bjoc.16.212

• increased the time required for the complete breakdown of the glycoside bond of the starting nucleoside. In order to find optimal conditions for the phosphorolysis reaction in the presence of Dowex-nPi, we analyzed some of the results of previous studies in terms of the role of the amount of bioсatalyst

Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

• Henrik Hupatz,
• Marius Gaedke,
• Hendrik V. Schröder,
• Julia Beerhues,
• Arto Valkonen,
• Fabian Klautzsch,
• Sebastian Müller,
• Felix Witte,
• Kari Rissanen,
• Biprajit Sarkar and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2020, 16, 2576–2588, doi:10.3762/bjoc.16.209

• alkali metal ions [2]. Crown ethers and their binding properties nowadays find frequent application, e.g., as cation sensors [4][5][6][7], as phase-transfer catalysts [8][9][10], or as drug delivery systems [11][12][13]. Already at the early stages of crown ether research, considerable effort has been

Comparative ligand structural analytics illustrated on variably glycosylated MUC1 antigen–antibody binding

• Christopher B. Barnett,
• Tharindu Senapathi and
• Kevin J. Naidoo

Beilstein J. Org. Chem. 2020, 16, 2540–2550, doi:10.3762/bjoc.16.206

• approach, we aim to use the tools and workflows available as part of the Galaxy project to analyze MD simulations to find out if the sugar moiety of the Tn-antigen binds directly to the antibody. Further, if the sugar does not bind directly (as found previously), then we will use these analyses to observe

Leveraging glycomics data in glycoprotein 3D structure validation with Privateer

• Haroldas Bagdonas,
• Daniel Ungar and
• Jon Agirre

Beilstein J. Org. Chem. 2020, 16, 2523–2533, doi:10.3762/bjoc.16.204

• distributed together with Privateer. If the existence of a glycan in the database is confirmed, then the software can attempt to find records about the sequence on other, more specialised databases (currently only GlyConnect) to obtain information such as the source organism, the type of glycosylation and the

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

• plans having different ranking orders we find that 5 out of 22 plans have +/− 1 rank positional change, 5 out of 22 plans have +/− 2 rank positional change, and 1 plan out of 22 having a +/− 3 rank positional change. Overall, the faster Borda count method is able to quickly identify the top and bottom

Hierarchically assembled helicates as reaction platform – from stoichiometric Diels–Alder reactions to enamine catalysis

• David Van Craen,
• Jenny Begall,
• Johannes Großkurth,
• Leonard Himmel,
• Oliver Linnenberg,
• Elisabeth Isaak and
• Markus Albrecht

Beilstein J. Org. Chem. 2020, 16, 2338–2345, doi:10.3762/bjoc.16.195

• helix induces the stereoselectivity of the Diels–Alder reaction. To find out which of the induction pathways takes over the control of the Diels–Alder reaction in the periphery of the helicates, a specific helicity was induced at an achiral diene bearing helicate. It has been described before that an

Formation of an exceptionally stable ketene during phototransformations of bicyclo[2.2.2]oct-5-en-2-ones having mixed chromophores

• Asitanga Ghosh

Beilstein J. Org. Chem. 2020, 16, 2297–2303, doi:10.3762/bjoc.16.190

• in moderate yields in acetone and acetonitrile solvents. However, we did not find an alternative 1,2-AS photoproduct. Even a change of the wavelength had no effect on the reactivity and similar results were obtained at 300 and 350 nm. The results are summarized in Table 2. The structures of ketenes

Tools for generating and analyzing glycan microarray data

• Akul Y. Mehta,
• Jamie Heimburg-Molinaro and
• Richard D. Cummings

Beilstein J. Org. Chem. 2020, 16, 2260–2271, doi:10.3762/bjoc.16.187

• comparison of glycan microarray data. We identify a variety of glycan microarray repositories where interested readers can find microarray data to build new software. We also highlight manual and automated data analysis tools. One must always be aware that the intrinsic complexity of the multistep process of

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

• was achieved with exclusive regioselectivity in peptides, with modest to moderate diastereomeric ratios of the fluorinated products (Scheme 29). With the optimum PSCat in hand, it was necessary to find a protecting group (PG) for the amine that would not undergo fluorination or oxidation when treated

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

• different N-glycoforms can be represented as a combination of spatial self-contained units, named “glycoblocks”, rather than in terms of monosaccharides and linkages. We find that this approach helps our understanding of N-glycans architecture in terms of equilibrium structures and relative populations and

Metal-free synthesis of phosphinoylchroman-4-ones via a radical phosphinoylation–cyclization cascade mediated by K₂S₂O₈

• Qiang Liu,
• Weibang Lu,
• Guanqun Xie and
• Xiaoxia Wang

Beilstein J. Org. Chem. 2020, 16, 1974–1982, doi:10.3762/bjoc.16.164

• phosphorus functionalities [27][28], thus combining the characteristics of both components in one molecule may find useful applications. However, there are only few ways to prepare such compounds. For example, in 2008 Rovis et al. [27] reported an intramolecular Stetter reaction of alkenyl aldehydes to

Synergy between supported ionic liquid-like phases and immobilized palladium N-heterocyclic carbene–phosphine complexes for the Negishi reaction under flow conditions

• Edgar Peris,
• Raúl Porcar,
• María Macia,
• Jesús Alcázar,
• Eduardo García-Verdugo and
• Santiago V. Luis

Beilstein J. Org. Chem. 2020, 16, 1924–1935, doi:10.3762/bjoc.16.159

• can be partially catched by the SILLP acting as scavenger. The key is to find out if these recaptured species onto SILLP are still active for the Negishi reaction. The leaching of Pd from NHC–Pd–RuPhos is in agreement with previous studies for C–C palladium catalyzed reactions [33][34][35]. Recently

Et₃N/DMSO-supported one-pot synthesis of highly fluorescent β-carboline-linked benzothiophenones via sulfur insertion and estimation of the photophysical properties

• Dharmender Singh,
• Vipin Kumar and
• Virender Singh

Beilstein J. Org. Chem. 2020, 16, 1740–1753, doi:10.3762/bjoc.16.146

• properties with quantum yield (ΦF) up to 47%. It is believed that these compounds may find applications in materials science and biomedical investigations. Conclusion In summary, an efficient synthesis of highly fluorescent β-carboline-linked benzothiophenone derivatives was successfully accomplished through

• yields (ΦF) of up to 47%. Detailed studies to synthesize novel fluorophores with improved optical properties which can easily find application in materials science are underway in our laboratory Experimental General experimental procedure for the synthesis of β-carboline-based 2-nitrochalcone derivatives