New efficient synthesis of polysubstituted 3,4-dihydroquinazolines and 4H-3,1-benzothiazines through a Passerini/Staudinger/aza-Wittig/addition/nucleophilic substitution sequence

• Long Zhao,
• Mao-Lin Yang,
• Min Liu and
• Ming-Wu Ding

Beilstein J. Org. Chem. 2022, 18, 286–292, doi:10.3762/bjoc.18.32

• of their derivatives [12][13][14][15][16][17][18][19][20][21][22]. For example (Scheme 1), a one-pot Tf2O-mediated assembly of amides, amines, and ketones provided 3,4-dihydroquinazolines in good yields via successive triflic anhydride-mediated amide dehydration, ketimine addition, and Pictet

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions

• Surendran Amrutha,
• Sankaran Radhika and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 262–285, doi:10.3762/bjoc.18.31

• ) moiety since it can easily undergo aggregation-induced emission enhancement (AIEE). The self-assembly of the HPB derivative resulted in the formation of fluorescent aggregates, which can act as a stabilizer or as a reactor for the development of α-Fe2O3 nanoparticles at room temperature. The catalytic

Synthesis and bioactivity of pyrrole-conjugated phosphopeptides

• Qiuxin Zhang,
• Weiyi Tan and
• Bing Xu

Beilstein J. Org. Chem. 2022, 18, 159–166, doi:10.3762/bjoc.18.17

• of 1. These results suggest that a heteroaromatic motif at the N-terminal of peptides likely disfavors the formation of extensive nanofibers or morphological changes during enzymatic self-assembly, thus provide useful insights for the development of phosphopeptides as substrates of phosphatases for

• controlling cell fate. Keywords: cells; enzyme; N-terminal; peptides; pyrroles; self-assembly; Introduction Biomacromolecular assemblies have received considerable attention recently in the field of biomaterials [1][2][3][4][5][6][7], among which peptides are of particular interest because of their unique

• ][11], collagen mimic [12], antibacterial [13][14], biomineralization [15][16], mimicry of amyloids [17], cell cultures [18], and tissue engineering [19]. Particularly, the use of enzyme-instructed self-assembly (EISA) [20][21] of peptide assemblies has expanded the applications of peptide assemblies

Earth-abundant 3d transition metals on the rise in catalysis

• Nikolaos Kaplaneris and
• Lutz Ackermann

Beilstein J. Org. Chem. 2022, 18, 86–88, doi:10.3762/bjoc.18.8

• , Germany 10.3762/bjoc.18.8 Keywords: C–H activation; 3d transition metals; green chemistry; late-stage functionalization; sustainability; Transition metal catalysis has emerged as a transformative platform for the assembly of increasingly complex compounds, with enabling applications to natural product

• industries as one of the most powerful methods for molecular assembly. With regard to the cost of goods and the allowance of trace metal impurities in medicinally relevant compounds, 3d transition metal complexes, such as those of iron, copper, cobalt or nickel, represent exciting, more sustainable

• functionalization enabled the de novo assembly of bioactive molecules [9]. The full potential of the mild nature of C–H functionalization is unlocked by the merger with modern photochemistry and electrocatalysis manifolds. In this context, recent advances were realized by the combination of photoredox catalysis and

Polymer chemistry: fundamentals and applications

• Bernhard V. K. J. Schmidt

Beilstein J. Org. Chem. 2021, 17, 2922–2923, doi:10.3762/bjoc.17.200

• supramolecular chemistry for the assembly of polymer fibers and the synthesis of well-defined polysaccharides. In the direction of materials, cryogels and reinforced hydrogels are discussed, as well as 3D-printed poly(caprolactone) biomaterials. In addition, properties of thermoresponsive materials and self

• -healing materials are presented in this thematic issue. Finally, the use of polymerization-induced self-assembly for the synthesis of drug carriers is presented. The issue also shows the multidisciplinary character of polymer science, for example when supramolecular motifs, organic coupling reactions or

Total synthesis of the O-antigen repeating unit of Providencia stuartii O49 serotype through linear and one-pot assemblies

• Tanmoy Halder and
• Somnath Yadav

Beilstein J. Org. Chem. 2021, 17, 2915–2921, doi:10.3762/bjoc.17.199

• involving the [1 + (1 + 1 = 2)] assembly, followed by a one-pot synthesis involving [1 + 1 + 1] strategy from the corresponding monosaccharides. The one-pot method provided a higher yield of the protected trisaccharide intermediate (73%) compared to the two step synthesis (66%). The protected trisaccharide

• co-worker accomplished the total synthesis of a O-polysaccharide of Providencia alcalifaciens O22 via a one pot assembly of the oligosaccharide unit [36]. Recently in 2020 Werz and co-workers completed the total synthesis of a tri-, hexa-, and heptasaccharide of the O-polysaccharide of Providencia

• the hitherto not synthesized above trisaccharide repeating unit containing two ᴅ-galactose and one N-acetyl-ᴅ-galactosamine moieties. The linear synthesis of the target oligosaccharide was first carried out via a linear [1 + (1 + 1 = 2)] assembly of a galactopyranose donor with a GalpNTroc–Galp

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

• reported a similar approach towards the assembly of 2,2-disubstituted indolines from N-sulfonylanilines and substituted styrene derivatives [93]. In 2014, the Jiao group investigated the carbosulfonation of alkenes 60 for the synthesis of oxindoles 90 through sequential C–S/C–C-bond formation (Scheme 16

• a four-component radical dual difunctionalization and ordered assembly of two chemically distinct alkenes 114/115, aldehyde 65, and tert-butyl peroxide (Scheme 23) [108]. In order to selectively couple one alkene to another, without the formation of oligomers, the authors utilized the different

Selective sulfonylation and isonitrilation of para-quinone methides employing TosMIC as a source of sulfonyl group or isonitrile group

• Chuanhua Qu,
• Run Huang,
• Yong Li,
• Tong Liu,
• Yuan Chen and
• Guiting Song

Beilstein J. Org. Chem. 2021, 17, 2822–2831, doi:10.3762/bjoc.17.193

• provides an efficient entry into the rapid assembly of various diarylmethyl sulfones and isonitrile diarylmethanes (Scheme 1C). Results and Discussion We commenced the study by using p-QMs 1a and TosMIC (2a) as model substrates to optimize the reaction conditions. As shown in Table 1, when 1a and 2a were

• assembling various diaryl methyl sulfones and isonitrile diarylmethanes. In the follow-up study, it was found that the isonitrile diarylmethanes are versatile building blocks for the rapid assembly of a series of compounds with novel structures. We are studying this part of the work. Experimental General

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

• bisamide derivatives that are both axially and centrally chiral (Scheme 28). Very recently, the same group reported the first CPA-catalyzed asymmetric assembly of axially chiral arylalkene-indole scaffolds by organocatalytic (Z/E)-selective and enantioselective (4 + 3)-cyclization using (3-alkynylindol-2

Adjusting the length of supramolecular polymer bottlebrushes by top-down approaches

• Tobias Klein,
• Franka V. Gruschwitz,
• Maren T. Kuchenbrod,
• Ivo Nischang,
• Stephanie Hoeppener and
• Johannes C. Brendel

Beilstein J. Org. Chem. 2021, 17, 2621–2628, doi:10.3762/bjoc.17.175

• methods represent an easily implementable technique toward 1D polymer nanostructures with an adjustable length in the range of interest for perspective biomedical applications. Keywords: distribution; dual centrifugation; filomicelles; self-assembly; ultrasonication; Introduction Cylindrical polymer

• desired applications in nanomedicine [4][5]. A key factor in this regard are formulation strategies, which allow a straightforward implementation into established processes that are, e.g., in accordance with good manufacturing practice (GMP) [6]. Approaches such as the crystallization-driven self-assembly

• the conditions for the assembly process, and are therefore often limited to specific materials. An alternative is the use of molecular motifs capable of forming directional supramolecular interaction forces, such as hydrogen bonds or π-interactions, to guide the one-dimensional (1D) assembly of

Isolation and characterization of new phenolic siderophores with antimicrobial properties from Pseudomonas sp. UIAU-6B

• Emmanuel T. Oluwabusola,
• Olusoji O. Adebisi,
• Fernando Reyes,
• Kojo S. Acquah,
• Mercedes De La Cruz,
• Larry L. Mweetwa,
• Joy E. Rajakulendran,
• Digby F. Warner,
• Deng Hai,
• Rainer Ebel and
• Marcel Jaspars

Beilstein J. Org. Chem. 2021, 17, 2390–2398, doi:10.3762/bjoc.17.156

• through deviation of the salimethyloxazolinyl-thioester intermediate 8 from the assembly line via an unusually facile C–N-bond opening of the ring to generate an ester bond, and followed directly by amination (+ NH3), the addition of histamine and phenethylamine units to form compounds 1, 2, and 3

Post-functionalization of drug-loaded nanoparticles prepared by polymerization-induced self-assembly (PISA) with mitochondria targeting ligands

• Janina-Miriam Noy,
• Fan Chen and
• Martina Stenzel

Beilstein J. Org. Chem. 2021, 17, 2302–2314, doi:10.3762/bjoc.17.148

• more structural investigations are required to elucidate this. Keywords: micelle; mitochondria; phosphorylcholine; PISA; polymerization-induced self-assembly; Introduction Targeting mitochondria is a promising strategy for the development of new anticancer drugs [1]. Among them, organoarsenical drugs

• suitability as a potential vehicle to deliver these drugs. Disadvantage is however the multistep procedure to generate micelles ranging from the synthesis of block copolymers to the self-assembly into micelles, often in low dilution, making the process inefficient. Micelles obtained by the PISA process can in

• contrast generate large amounts of nanoparticles in a reproducible manner. PISA nanoparticles have been frequently investigated as drug carriers. The challenge is often how to entrap the drug during the self-assembly process. Addition of drugs during the PISA process is possible [33][34], but it needs to

Photoredox catalysis in nickel-catalyzed C–H functionalization

• Lusina Mantry,
• Rajaram Maayuri,
• Vikash Kumar and
• Parthasarathy Gandeepan

Beilstein J. Org. Chem. 2021, 17, 2209–2259, doi:10.3762/bjoc.17.143

• this protocol using the chiral iPrBiOx ligand under slightly modified reaction conditions (Scheme 19) [72]. Recently, Chu achieved the selective assembly of vinyl and aryl functionalities onto saturated cyclic hydrocarbons via a photoredox nickel-catalyzed sequential C–O decarboxylative vinylation

Constrained thermoresponsive polymers – new insights into fundamentals and applications

• Patricia Flemming,
• Alexander S. Münch,
• Andreas Fery and
• Petra Uhlmann

Beilstein J. Org. Chem. 2021, 17, 2123–2163, doi:10.3762/bjoc.17.138

• physicochemical interplay between the architecture of the polymer assembly and the resulting thermoresponsive switching behavior will be in the foreground of this consideration. Keywords: lower critical solution temperature (LCST); responsive coating; smart material; thermoresponsive polymer; upper critical

• -assembly due to their structure consisting of hydrophilic and hydrophobic units [110][111][112][113]. In the case of rather large corona blocks compared to the core-forming blocks, such structures are usually star-shaped and spherically composed of many individual chains by noncovalent interchain

• absolute length of the block copolymer and the relative length of the blocks to each other and the glass transition temperature. If a block is composed of a thermoresponsive polymer, the amphiphilic character and self-assembly ability can be altered by changing the temperature. The thermoresponsive block

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

• approach (also known as fragment coupling) allows connecting pre-assembled oligosaccharide blocks. To decrease the synthetic time required for the chemical synthesis of polysaccharides, automated techniques have been developed [28][29][30][31]. Automated glycan assembly (AGA) connects monosaccharide BBs on

• a solid support following a linear approach (Figure 1D). Cycles of glycosylation and selective deprotection are iteratively performed to access the desired polysaccharide with full control over the length and the monosaccharide sequence [32]. Upon completion of the assembly, the desired product is

• of the self-assembly of cellulose chains at the active site of the enzyme suggested that diffusion of the aggregated molecules and the monomers around the active center dictates the DP that can be obtained by enzymatic polymerization [70][71]. This could be the reason causing enzymatic reactions to

Asymmetric organocatalyzed synthesis of coumarin derivatives

• Natália M. Moreira,
• Lorena S. R. Martelli and
• Arlene G. Corrêa

Beilstein J. Org. Chem. 2021, 17, 1952–1980, doi:10.3762/bjoc.17.128

• multicomponent reaction (IMCR) [31]. The enantioenriched hemiacetals 5 were obtained using the Jørgensen catalyst 7 as previously described by Rueping et al. [32]. This approach enables the rapid assembly of complex natural product hybrids 6 including up to four different molecular fragments, such as

Cationic oligonucleotide derivatives and conjugates: A favorable approach for enhanced DNA and RNA targeting oligonucleotides

• Mathias B. Danielsen and
• Jesper Wengel

Beilstein J. Org. Chem. 2021, 17, 1828–1848, doi:10.3762/bjoc.17.125

• amine functionalities in their neutral, i.e., non-protonated form. Regarding synthetic strategies, both the use of amine group functionalized phosphoramidites, i.e., functionalized monomeric building blocks, as well as conjugation with amine groups after completion of the ON assembly, are being

Volatile emission and biosynthesis in endophytic fungi colonizing black poplar leaves

• Christin Walther,
• Pamela Baumann,
• Katrin Luck,
• Beate Rothe,
• Peter H. W. Biedermann,
• Jonathan Gershenzon,
• Tobias G. Köllner and
• Sybille B. Unsicker

Beilstein J. Org. Chem. 2021, 17, 1698–1711, doi:10.3762/bjoc.17.118

• contribute to the overall (E)-β-caryophyllene emission from the tree. To identify terpene synthase genes potentially involved in volatile terpene formation in Cladosporium, we sequenced the transcriptome and performed a de novo assembly of the obtained reads. A TBLASTN analysis with Aspergillus terreus

• aristolochene synthase (pdb 20A6) as query and the de novo assembly as template revealed two genes with high similarity to other fungal TPS genes. The genes were designated CxTPS1 and CxTPS2. For functional characterization, the complete open reading frames of CxTPS1 and CxTPS2 were amplified from cDNA, cloned

• library was prepared, and PolyA enrichment was performed before sequencing on an IlluminaHiSeq 3000 sequencer (Max Planck Genome Centre, Cologne, Germany) with 25 Mio reads, 150 base pairs, paired end. Trimming of the obtained Illumina reads and de novo assembly were both performed with the program CLC

Chemical approaches to discover the full potential of peptide nucleic acids in biomedical applications

• Nikita Brodyagin,
• Martins Katkevics,
• Venubabu Kotikam,
• Christopher A. Ryan and
• Eriks Rozners

Beilstein J. Org. Chem. 2021, 17, 1641–1688, doi:10.3762/bjoc.17.116

• hairpin structure in the 5’-UTR of an mRNA, which inhibited ribosome assembly and suppressed mRNA translation in vitro and in cells [119]. This study was the first demonstration of the biological effect of binding of M- and P-modified PNAs to dsRNA in live cells. Recent work from our labs [120

Copper-mediated oxidative C−H/N−H activations with alkynes by removable hydrazides

• Feng Xiong,
• Bo Li,
• Chenrui Yang,
• Liang Zou,
• Wenbo Ma,
• Linghui Gu,
• Ruhuai Mei and
• Lutz Ackermann

Beilstein J. Org. Chem. 2021, 17, 1591–1599, doi:10.3762/bjoc.17.113

• : benzhydrazides; copper; 3-methyleneisoindolin-1-one; removable directing group; Introduction Inexpensive copper-promoted oxidative C−H activations [1][2][3][4][5][6][7][8][9][10][11] have been recognized as competent tools for the efficient assembly and late-stage functionalization of organic molecules due to

• (Cq), 129.3 (CH), 128.7 (CH), 127.3 (CH), 127.3 (CH), 126.5 (Cq), 123.8 (CH), 119.8 (CH), 114.3 (CH), 107.8 (CH), 106.4 (CH), 36.7 (CH3); HRESIMS (m∕z): [M + H]+ calcd for C21H18N3O, 328.1444; found, 328.1439. Assembly of 3-methyleneisoindolin-1-one via 3d transition metal-mediated/catalyzed oxidative

Recent advances in the application of isoindigo derivatives in materials chemistry

• Andrei V. Bogdanov and
• Vladimir F. Mironov

Beilstein J. Org. Chem. 2021, 17, 1533–1564, doi:10.3762/bjoc.17.111

• composite with platinum nanoparticles stabilized with poly(acrylic acid) [113]. Such a catalytic system, obtained by layer-by-layer self-assembly with the addition of poly(diallyldimethylammonium chloride) on the indium tin oxide surface, provided hydrogen formation in photoelectrolytic cycles with a

Free-radical cyclization approach to polyheterocycles containing pyrrole and pyridine rings

• Ivan P. Mosiagin,
• Olesya A. Tomashenko,
• Dar’ya V. Spiridonova,
• Mikhail S. Novikov,
• Sergey P. Tunik and
• Alexander F. Khlebnikov

Beilstein J. Org. Chem. 2021, 17, 1490–1498, doi:10.3762/bjoc.17.105

• , attempts to assemble this framework using Pd-catalyzed intramolecular arylation of compounds C' (X = Br, I) failed [17]. In this work, we report an effective method for the assembly of pyrido[2,1-a]pyrrolo[3,4-c]isoquinoline and related frameworks via a free radical cyclization of pyrrolylpyridinium salts

Cascade intramolecular Prins/Friedel–Crafts cyclization for the synthesis of 4-aryltetralin-2-ols and 5-aryltetrahydro-5H-benzo[7]annulen-7-ols

• Jie Zheng,
• Shuyu Meng and
• Quanrui Wang

Beilstein J. Org. Chem. 2021, 17, 1481–1489, doi:10.3762/bjoc.17.104

• the assembly of complex molecules from relatively simple and inexpensive materials/reagents in a single operation. The reaction continues to be an interesting and profitable field of research with high impact on synthetic organic chemistry [17][18]. Many of the existing protocols rely on an acid

Antiviral therapy in shrimp through plant virus VLP containing VP28 dsRNA against WSSV

• Santiago Ramos-Carreño,
• Ivone Giffard-Mena,
• Jose N. Zamudio-Ocadiz,
• Alfredo Nuñez-Rivera,
• Ricardo Valencia-Yañez,
• Jaime Ruiz-Garcia,
• Maria Teresa Viana and
• Ruben D. Cadena-Nava

Beilstein J. Org. Chem. 2021, 17, 1360–1373, doi:10.3762/bjoc.17.95

• entry, binding and assembly of the virion. Previous studies have shown that silencing these structural proteins in WSSV challenge assays, increases shrimp survival [10][11][17][18][19][20][21]. The VP28 glycoprotein plays an important role in systemic infection by interacting with cell membrane proteins

• assembling. SDS-PAGE was used to verify the integrity of the capsid protein. In vitro assembly of VLPs-dsRNAvp28. Dissociated CCMV CP and dsRNAvp28 were mixed in a mass ratio of 6:1 (CP/dsRNA) and dialyzed overnight against RNA assembly buffer (50 mM NaCl, 10 mM KCl, 5 mM MgCl2, 50 mM Tris-HCl, pH 7.2) at 4

• °C. The samples were acidified by dialysis in virus suspension buffer (50 mM sodium acetate, 8 mM magnesium acetate, pH 4.5) for at least 4 hours. Then, to disrupt the empty capsids, the sample was dialyzed against an RNA assembly buffer. The VLP-dsRNAvp28 was then purified and concentrated by

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

• represents a family of materials where variety of synthetic routes can be applied to form photoactive matter with altered properties, i.e., monomer supramolecular assembly to attain a monomer complex prior to carbonization results in enhanced porosity and photoactivity since ordered structures are formed