Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

• Naoki Miyamoto,
• Daichi Koseki,
• Kohei Sumida,
• Elghareeb E. Elboray,
• Naoko Takenaga,
• Ravi Kumar and
• Toshifumi Dohi

Beilstein J. Org. Chem. 2024, 20, 1020–1028, doi:10.3762/bjoc.20.90

• modifying their physical properties, and stability and controlling the reactivity of arylation processes, as demonstrated in various studies [9][10]. For instance, the Gaunt group reported that the use of a fluoride counterion in diaryliodonium(III) salt can trigger phenol O-arylation by activating the

• )iodonium(III) carboxylate 7ai in 86% yield, opening up new avenues for structural modifications of drug candidates to improve their properties and consequently, bioactivities [38][39][40]. The umbelliferone-3-carboxylic acid derivative 6j was also employed to produce the phenyl(TMP)iodonium(III

Spin and charge interactions between nanographene host and ferrocene

• Akira Suzuki,
• Yuya Miyake,
• Ryoga Shibata and
• Kazuyuki Takai

Beilstein J. Org. Chem. 2024, 20, 1011–1019, doi:10.3762/bjoc.20.89

• of the charge transfer from ferrocene to CNTs was estimated from the shift of peaks for van Hove singularities in the valence-band photoemission spectrum [19][20]. The magnetic properties of ferrocene encapsulated into CNTs have also been investigated by superconducting quantum interference devices

Carbonylative synthesis and functionalization of indoles

• Alex De Salvo,
• Raffaella Mancuso and
• Xiao-Feng Wu

Beilstein J. Org. Chem. 2024, 20, 973–1000, doi:10.3762/bjoc.20.87

• heterocyclization reactions by exploiting the electrophilic character of Pd(II) species. Starting from substrates bearing a triple bond and a nucleophile in the appropriate position, a versatile process of heterocyclization can be initiated, resulting in indole derivatives with important properties. Gabriele et al

Enhancing structural diversity of terpenoids by multisubstrate terpene synthases

• Min Li and
• Hui Tao

Beilstein J. Org. Chem. 2024, 20, 959–972, doi:10.3762/bjoc.20.86

• properties (Figure 4c) [45]. Notably, one tetrahydrofuranoterpenoid 59 is also formed as a major product in the BcBoT2 reaction, despite the low sequence similarity between these sesqui-TSs, which could be explained by similar active-site conformations to stabilize prenyl substrates. Similarly, limonene

• products, 3-ethyl-3-buten-1-ol (139) and 3-propyl-3-buten-1-ol (140), have potent fuel properties, highlighting the potential of this strategy for producing isoprenol analogs as next-generation biofuels (Figure 10b) [62]. Conclusion During terpenoid biosynthesis, most TSs have strict substrate selectivity

Innovative synthesis of drug-like molecules using tetrazole as core building blocks

• Jingyao Li,
• Ajay L. Chandgude,
• Qiang Zheng and
• Alexander Dömling

Beilstein J. Org. Chem. 2024, 20, 950–958, doi:10.3762/bjoc.20.85

• 1H-tetrazole as a bioisostere for carboxylic acid has long been recognized for its potential in enhancing drug-like properties [37]. Predominantly, tetrazoles are currently introduced by a late-stage-functionalization approach from their nitrile precursors. This work, however, takes an additional

Direct synthesis of acyl fluorides from carboxylic acids using benzothiazolium reagents

• Lilian M. Maas,
• Alex Haswell,
• Rory Hughes and
• Matthew N. Hopkinson

Beilstein J. Org. Chem. 2024, 20, 921–930, doi:10.3762/bjoc.20.82

• of all these properties mean that acyl fluorides can provide significant advantages over acyl chlorides, especially for challenging acylation reactions [13][14]. Nevertheless, acyl chlorides still dominate in the literature; however, the recent development of safer and more practical synthetic routes

One-pot Ugi-azide and Heck reactions for the synthesis of heterocyclic systems containing tetrazole and 1,2,3,4-tetrahydroisoquinoline

• Jiawei Niu,
• Yuhui Wang,
• Shenghu Yan,
• Yue Zhang,
• Xiaoming Ma,
• Qiang Zhang and
• Wei Zhang

Beilstein J. Org. Chem. 2024, 20, 912–920, doi:10.3762/bjoc.20.81

• ; Introduction Tetrazole is a privileged heterocycle existing in a range of biological and medicinally interesting compounds [1][2] with antifungal [3][4], antibacterial [5], anticancer [6][7], antiparasitic [8], and antihypertensive properties [9] including FDA approved drugs such as valsartan and cefmetazole

Synthesis and properties of 6-alkynyl-5-aryluracils

• Ruben Manuel Figueira de Abreu,
• Till Brockmann,
• Alexander Villinger,
• Peter Ehlers and
• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 898–911, doi:10.3762/bjoc.20.80

• of different functional groups was tested. The influence of different functional groups on the physical properties was studied by ultraviolet–visible (UV–vis) and fluorescence spectroscopy, providing new insights into the potential applications of uracil-based structures. Keywords: catalysis; cross

• therefore plays a very important role in many vital biological processes in the human body and other life forms. Uracil is rarely found in DNA, due to its lower stability and mutagenic properties when mismatched with guanine [2][3][4][5]. This fact can be used to differentiate between RNA and DNA-dependent

• a targeted enzyme [21][22][23]. One of these focus areas was the synthesis of alkyne-linked derivatives. The first alkyne-linked compound was already published in 1976, accompanied by new synthesis methods in the following years [24][25][26][27]. With the discovery of potential antiviral properties

(Bio)isosteres of ortho- and meta-substituted benzenes

• H. Erik Diepers and
• Johannes C. L. Walker

Beilstein J. Org. Chem. 2024, 20, 859–890, doi:10.3762/bjoc.20.78

• H. Erik Diepers Johannes C. L. Walker Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany 10.3762/bjoc.20.78 Abstract Saturated bioisosteres of substituted benzenes offer opportunities to fine-tune the properties of drug

• well as the impact they have on the physiochemical and biological properties of pharmaceuticals and agrochemicals. Keywords: bioisosteres; drug discovery; meta-benzene; ortho-benzene; Introduction The logical and iterative modification of the structure of a drug candidate is a critical part of the

• early drug discovery process. In many cases, the primary aim is the enhancement of biological activity, but in others, modulation of other critical properties such as aqueous solubility, metabolic stability, polarity, or lipophilicity is the target. In the latter cases, there is often a desire to retain

Ortho-ester-substituted diaryliodonium salts enabled regioselective arylocyclization of naphthols toward 3,4-benzocoumarins

• Ke Jiang,
• Cheng Pan,
• Limin Wang,
• Hao-Yang Wang and
• Jianwei Han

Beilstein J. Org. Chem. 2024, 20, 841–851, doi:10.3762/bjoc.20.76

• [31][32][33]. Building on our great interest in ortho-functionalized diaryliodonium salts and their dual activation capabilities, we sought to incorporate carboxylic ester groups into the structures of ortho-substituted diaryliodonium salts to explore their properties and reactivity. Our previous

Synthesis and characterization of water-soluble C₆₀–peptide conjugates

• Yue Ma,
• Lorenzo Persi and
• Yoko Yamakoshi

Beilstein J. Org. Chem. 2024, 20, 777–786, doi:10.3762/bjoc.20.71

• unique structure of fullerenes, characterized by a fully conjugated closed-cage structure, containing a mixture of hexagonal and pentagonal rings, have been recognized for the unique electronic [2][3][4], optical [5][6], and mechanical properties [7][8]. Despite the notable achievements in fullerene

Synthesis of new representatives of A₃B-type carboranylporphyrins based on meso-tetra(pentafluorophenyl)porphyrin transformations

• Victoria M. Alpatova,
• Evgeny G. Rys,
• Elena G. Kononova and
• Valentina A. Ol'shevskaya

Beilstein J. Org. Chem. 2024, 20, 767–776, doi:10.3762/bjoc.20.70

• aromatic substitution; Introduction Porphyrins are available macroheterocyclic compounds which play an important role in diverse areas of scientific research owing to their unique photophysical, electrochemical, and optical properties [1]. They have been widely studied in biomedical applications, as

• biomacromolecule [10][11]. In this context, fluorinated porphyrins have attracted considerable interest due to their biological properties such as low toxicity, metabolic stability, and cellular uptake. The introduction of a fluorine atom into the molecule is the feasibility to change drastically its biological

• properties and to modify the profile of biological activity due to optimum fluorine lipophylic properties, and enhanced interaction with lipid membranes [12][13][14]. Pentafluorophenyl-substituted porphyrin systems are especially useful for the connection of various functionalities capable for coupling with

Research progress on the pharmacological activity, biosynthetic pathways, and biosynthesis of crocins

• Zhongwei Hua,
• Nan Liu and
• Xiaohui Yan

Beilstein J. Org. Chem. 2024, 20, 741–752, doi:10.3762/bjoc.20.68

• -inflammatory properties, hepatorenal protection, and anticancer activity. They are often used as coloring and seasoning agents. Due to the limited content of crocins in plants and the high cost of chemical synthesis, the supply of crocins is insufficient to meet current demand. The biosynthetic pathways for

• pharmaceutical industries [5]. They exhibit a broad spectrum of pharmacological activity, including antitumor [6], anti-inflammatory [7], hepatoprotective [8], nephroprotective [9], antidepressant [10], antioxidant [11], and antidiabetic [12] properties. The Saffron Multi-glycoside Tablet (Xihonghua Zonggan Pian

• heterologous production of crocins in microorganisms to break the current bottleneck of a sustainable supply. It provides the basis for the further development of crocins in the food, cosmetic, and pharmaceutical industries. Review Chemical properties and distribution of crocins More than ten crocins have been

SOMOphilic alkyne vs radical-polar crossover approaches: The full story of the azido-alkynylation of alkenes

• Julien Borrel and
• Jerome Waser

Beilstein J. Org. Chem. 2024, 20, 701–713, doi:10.3762/bjoc.20.64

• the development of the azidobenziodazolone scaffold [17]. This class of derivative showed an improved safety profile while retaining the redox properties of the original reagent. A single example of azido-alkynylation has been reported by Ramasastry and co-workers during a mechanistic study for an

New variochelins from soil-isolated Variovorax sp. H002

• Jabal Rahmat Haedar,
• Aya Yoshimura and
• Toshiyuki Wakimoto

Beilstein J. Org. Chem. 2024, 20, 692–700, doi:10.3762/bjoc.20.63

• cereus and Kocuria rhizophila. We subsequently investigated the antimicrobial properties of 1 against several known Gram-negative plant pathogens isolated from the same collection site as Variovorax sp. H002. Remarkably, variochelin A (1) moderately inhibited seven out of eight tested plant pathogens

Enhanced reactivity of Li⁺@C₆₀ toward thermal [2 + 2] cycloaddition by encapsulated Li⁺ Lewis acid

• Hiroshi Ueno,
• Yu Yamazaki,
• Hiroshi Okada,
• Fuminori Misaizu,
• Ken Kokubo and
• Hidehiro Sakurai

Beilstein J. Org. Chem. 2024, 20, 653–660, doi:10.3762/bjoc.20.58

• the burgeoning family of ion-endohedral fullerenes, holds substantial promise for diverse applications owing to its distinctive ionic properties. Despite the high demand for precise property tuning through chemical modification, there have been only a few reports detailing synthetic protocols for the

• progress in synthetic procedures has contributed to diversifying their properties, enabling widespread and interdisciplinary applications in various research fields, such as biomedicine, photovoltaic devices, and materials chemistry. Meanwhile, lithium ion-endohedral fullerenes (Li+@C60) [8], the first

• member of the emerging ion-endohedral fullerene family, have attracted significant attention owing to the distinctive ionic properties originating from the ion pair structure consisting of a cationic endohedral fullerene core and an external counter anion. Despite being a relatively recent addition, Li

Production of non-natural 5-methylorsellinate-derived meroterpenoids in Aspergillus oryzae

• Jia Tang,
• Yixiang Zhang and
• Yudai Matsuda

Beilstein J. Org. Chem. 2024, 20, 638–644, doi:10.3762/bjoc.20.56

• Jia Tang Yixiang Zhang Yudai Matsuda Department of Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong SAR, China 10.3762/bjoc.20.56 Abstract Fungal meroterpenoids are diverse structurally intriguing molecules with various biological properties. One large group within

HPW-Catalyzed environmentally benign approach to imidazo[1,2-a]pyridines

• Luan A. Martinho and
• Carlos Kleber Z. Andrade

Beilstein J. Org. Chem. 2024, 20, 628–637, doi:10.3762/bjoc.20.55

• attractive intrinsic properties, HPW was used in our initial studies to find the best reaction conditions. Additionally, knowing that a higher temperature is crucial for faster GBB reactions, μw heating was used, taking into account our experience over the years on the μw-mediated MCRs [51][52][53]. 2

A laterally-fused N-heterocyclic carbene framework from polysubstituted aminoimidazo[5,1-b]oxazol-6-ium salts

• Andrew D. Gillie,
• Matthew G. Wakeling,
• Bethan L. Greene,
• Louise Male and
• Paul W. Davies

Beilstein J. Org. Chem. 2024, 20, 621–627, doi:10.3762/bjoc.20.54

• contrast to the most widely used ‘umbrella-like’ NHCs (Figure 1) [2][3]. An extended π-system influences the donor and acceptor properties of the carbene whilst substitution on the polycycle can position groups adjacent to the active centre. The imidazo[1,5-a]pyridin-3-ylidene motif (ImPy), independently

• sphere, accessing more diverse fused imidazolium frameworks and different peripheral functionality offers significant scope to influence catalytic properties. Few studies into L-shaped imidazolylidines have explored core motifs beyond ImPy, with NHCs derived from two π-rich rings fused together

Chemical and biosynthetic potential of Penicillium shentong XL-F41

• Ran Zou,
• Xin Li,
• Xiaochen Chen,
• Yue-Wei Guo and
• Baofu Xu

Beilstein J. Org. Chem. 2024, 20, 597–606, doi:10.3762/bjoc.20.52

• . Researchers have identified numerous compounds with anticancer properties, including mycophenolic acid, brefeldin A, and wortmannin [3], as well as compounds with antibacterial properties like xestodecalactones A–C, penicifurans A, and anthraquinone-citrinin [4]. From 2010 to 2022, researchers have identified

• over 260 secondary metabolites from Penicillium [5], exhibiting not only antibacterial and anticancer activities but also potent antioxidant properties, inhibition of GSK-3β and α-glucosidase activities, and interaction with the pregnane X receptor (PXR). These compounds are categorized into

• , and anticancer properties [6][7]. Historically, most alkaloids were isolated from higher plants, with a significant number found in the Apocynaceae family. Notable examples such as vinblastine, vinorelbine, vincristine, and vindesine have gained prominence as effective anticancer drugs [6][7][8][9][10

Recent developments in the engineered biosynthesis of fungal meroterpenoids

• Zhiyang Quan and
• Takayoshi Awakawa

Beilstein J. Org. Chem. 2024, 20, 578–588, doi:10.3762/bjoc.20.50

• , including the known antitumor compound subglutinol A (16) (Figure 3A and B) [17]. Among the novel compounds isolated from the production system, some exhibited intruiging pharmacological activities, such as antitumor (16), anti-HIV activity (17), and anti-Alzheimer's disease properties (18). Furthermore

Possible bi-stable structures of pyrenebutanoic acid-linked protein molecules adsorbed on graphene: theoretical study

• Yasuhiro Oishi,
• Motoharu Kitatani and
• Koichi Kusakabe

Beilstein J. Org. Chem. 2024, 20, 570–577, doi:10.3762/bjoc.20.49

• to carbon materials [2][3]. The properties and characteristics of these linker molecules are keys not only to the purpose of protein immobilization, but also to the behavior of the entire biosensor system. In oscillator-based biosensors, further adsorption on the sensor, such as viruses using antigen

• . Rotations around each bond can also happen and we expect similar steric hindrance effects to appear. Mechanical properties of PBA-linked molecular structure on graphene Here, we discuss possible conformations of the PBA-linked molecule. Would a similar activation barrier-type potential energy surface be

• vibrational properties of elastic waves, such as phase and amplitude, are known to be highly sensitive to the mass of adsorbed materials on multilayered graphene. Recently, a biosensor that detects target antigens by elastic wave measurement has been developed [11][12], using the method of immobilizing an

Entry to new spiroheterocycles via tandem Rh(II)-catalyzed O–H insertion/base-promoted cyclization involving diazoarylidene succinimides

• Alexander Yanovich,
• Anastasia Vepreva,
• Ksenia Malkova,
• Grigory Kantin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2024, 20, 561–569, doi:10.3762/bjoc.20.48

• activity) [16], ramariolide A (antitubercular) [17], (+)-massarinolin A (antibacterial) [18], anemonin (antiparasitic) [19], (+)-pyrenolide D (cytotoxic) [20], and (+)-crassalactone D (antitumor) [21]. Synthetic or semisynthetic spiro Δα,β-butenolides have also shown a range of biological properties

• properties are exhibited by compounds based on a THF and THP core spiro-conjugated with the pyrrolidine ring. These frameworks are present in a number of synthetic biologically active compounds (such as NaV1.7 blocker XEN907 for the treatment of pain [31], σ1 receptor ligand 6 [32], histamine-3 receptor

Synthesis of photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2Н)-ones with a terminal phenanthroline group

• Vladimir P. Rybalkin,
• Sofiya Yu. Zmeeva,
• Lidiya L. Popova,
• Irina V. Dubonosova,
• Olga Yu. Karlutova,
• Oleg P. Demidov,
• Alexander D. Dubonosov and
• Vladimir A. Bren

Beilstein J. Org. Chem. 2024, 20, 552–560, doi:10.3762/bjoc.20.47

• change of the solutions from yellow to dark orange. Subsequent selective interaction with AcO− led to the restoration of the initial absorption and emission properties. Thus, the obtained compounds represent dual-mode “on–off–on” switches of optical and fluorescent properties under sequential exposure to

• absorption spectra, induced in one or both directions by absorption of electromagnetic radiation [1][2][3][4]. Due to the different structures and the different optical and emission properties of these forms, photochromic compounds are used in 3D optical memory devices, photoswitches of different types

• inverse photochromism), such as merocyanine forms of spiropyrans and spirooxazines, azomethine imines, thioindigoid dyes and N→O acylotropic systems [12][13][14][15]. Recently, they have been actively used to create next-generation molecular switches, materials with new properties (in particular, color

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

• because of the simple design and high potential for many applications. The drastic conformational change induced by the opening and closing of the tweezers attracted us as a straightforward method to control various properties. This change creates a cavity for guest binding, but tweezers have even greater

• potential if the arms exhibit additional properties such as luminescence, magnetism, catalysis, redox activity, or more. Such systems can also provide two orthogonal responses: the mechanical motion between the open and closed forms, and a potential new property that emerges when the arms are in spatial

• et al. exploited the same scaffold to control the physical properties of materials. They incorporated planar terpyridine-alkyne Pt complexes as functional units and studied the intercalation of a Pt-complex guest in order to obtain Pt–Pt interactions in solution [23]. In the native state of 3, both