Recent advances in the electrochemical synthesis of organophosphorus compounds

• Babak Kaboudin,
• Milad Behroozi,
• Sepideh Sadighi and
• Fatemeh Asgharzadeh

Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61

• on silver-catalyzed C–H phosphorylation revealed that variations in current intensity, frequency, and duty ratio influence product yield. To achieve optimal reactivity, the duty ratio must exceed 50%. Additionally, an analysis of silver deposition on carbon and platinum electrodes indicated that

• proceeded smoothly without Et3N or acetate, indicating that these compounds do not play a role in the reaction process (Table 2). To study ferrocene's electrochemical direct phosphorylation reaction with diphenylphosphine oxide, Chen et al. [49] examined and reported electrochemical C–P bond formation of

• anode at a constant current at 50 °C in methanol for 6 h. This method also obtained a small amount of over-phosphorylated products. Phosphorylation occurred even when no functional group was present at the α-position of the aryl ring. Products with good yields were synthesized despite methyl, bromine

Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations

• Seungmin Lee,
• Minsuk Kim,
• Hyewon Han and
• Jongwoo Son

Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12

• desired N-arylamide 13 is yielded through protodemetalation. In this process, copper does not undergo further catalytic turnover, presumably due to the formation of inactive copper fluoride or copper hydroxide species. 1.5 N-Phosphorylation of dioxazolones Recently, Son and Kuniyil reported the N

• -phosphorylation of dioxazolones using organic phosphines and copper catalysts [91]. As shown in Scheme 6, a variety of dioxazolones 14 were explored for the synthesis of N-acyl iminophosphoranes 16. Dioxazolones containing aryl and heteroaryl groups were successfully transformed into the desired products in high

Advances in radical peroxidation with hydroperoxides

• Oleg V. Bityukov,
• Pavel Yu. Serdyuchenko,
• Andrey S. Kirillov,
• Gennady I. Nikishin,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249

N-Glycosides of indigo, indirubin, and isoindigo: blue, red, and yellow sugars and their cancerostatic activity

• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 2840–2869, doi:10.3762/bjoc.20.240

• , and Parkinson's disease, cardiovascular diseases, inflammation, AIDS and others have their origin in context with the activities of protein kinases, such as glycogen synthase kinase-3 (GSK-3β) and cyclin-dependent kinases (CDK’s). The phosphorylation of the amino acid moieties of several enzymes is

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

• anodic oxidation. In addition to ruthenium-catalyzed electrochemically mediated C–H functionalizations, several groups have also explored rhodium-catalyzed anodic oxidation reactions [52][53]. Wen, Zhang, Xu, and colleagues described an efficient method for the phosphorylation of aryl substrates

• utilizing a Rh(III) catalyst [54]. The critical step in this process is the anodic oxidation of Rh(III) to a high-valent Rh complex on the RVC anode. This transformation necessitates the presence of a directing group in the substrate molecule. Cyclic ketimine was found to direct ortho-C–H phosphorylation

Natural resorcylic lactones derived from alternariol

• Joachim Podlech

Beilstein J. Org. Chem. 2024, 20, 2171–2207, doi:10.3762/bjoc.20.187

Computational toolbox for the analysis of protein–glycan interactions

• Ferran Nieto-Fabregat,
• Maria Pia Lenza,
• Angela Marseglia,
• Cristina Di Carluccio,
• Antonio Molinaro,
• Alba Silipo and
• Roberta Marchetti

Beilstein J. Org. Chem. 2024, 20, 2084–2107, doi:10.3762/bjoc.20.180

• mammalian glycans rely on a group of “only” 10 monosaccharide units, they can be assembled, in linear or branched chains, through different glycosidic linkages and diverse spatial orientations, which can also undergo modifications, such as methylation, sulfation, and phosphorylation, resulting in a plethora

Harnessing the versatility of hydrazones through electrosynthetic oxidative transformations

• Aurélie Claraz

Beilstein J. Org. Chem. 2024, 20, 1988–2004, doi:10.3762/bjoc.20.175

• aldehyde-derived hydrazones 114 and diarylphosphine oxide 115. The phosphorylation proceeded with slightly higher yield in the presence of a catalytic amount of manganese dibromide but its role was not clearly identified. Cyclic voltammetry analysis supported the initial oxidation of the hydrazone (Ep/2 of

• ].· Synthesis of 1,2,3-thiadiazoles [64]. Synthesis of 5-thioxo-1,2,4-triazolium inner salts [65]. Synthesis of 1-aminotetrazoles [66]. C(sp2)–H functionalization of aldehyde-derived hydrazones: general mechanisms. C(sp2)–H functionalization of benzaldehyde diphenyl hydrazone [68][69]. Phosphorylation of

Syntheses and medicinal chemistry of spiro heterocyclic steroids

• Laura L. Romero-Hernández,
• Ana Isabel Ahuja-Casarín,
• Penélope Merino-Montiel,
• Sara Montiel-Smith,
• José Luis Vega-Báez and
• Jesús Sandoval-Ramírez

Beilstein J. Org. Chem. 2024, 20, 1713–1745, doi:10.3762/bjoc.20.152

Functions of enzyme domains in 2-methylisoborneol biosynthesis and enzymatic synthesis of non-natural analogs

• Binbin Gu,
• Lin-Fu Liang and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2023, 19, 1452–1459, doi:10.3762/bjoc.19.104

• obtained through standard phosphorylation of the corresponding known alcohols [35][36][37]. In a first screening, these derivatives were tested in all possible combinations in small scale reactions (0.3 mg of each substrate) with FPPS. The results were investigated through dephosphorylation with calf

• ). The combined extracts were dried with MgSO4 and concentrated under reduced pressure to afford the bromide, which was used for phosphorylation without purification. (NBu4)3HP2O7 (4.02 g, 4.46 mmol, 1.5 equiv) was dissolved in acetonitrile (1 mL), and the bromide (mixed with 10 mL acetonitrile) was

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

• catalyst generation for the reduction of aryl halides. Compared to conPET chemistry with organic photocatalysts, no terminal reductants like trialkylamines or formates were required for redox-neutral transformations like the C–H arylation, borylation or phosphorylation owing to the interplay between the

Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities

• Jorge de Lima Neto and
• Paulo Henrique Menezes

Beilstein J. Org. Chem. 2023, 19, 399–427, doi:10.3762/bjoc.19.31

• to improve the water solubility of combretastatin D-2 (2) by converting it into a series of phosphate salts and other prodrugs. Thus, phosphorylation of combretastatin D-2 (2) using dibenzyl phosphite gave derivative 183. Further cleavage of the benzyl groups using TMSBr followed by the reaction of

A new route for the synthesis of 1-deazaguanine and 1-deazahypoxanthine

• Raphael Bereiter,
• Marco Oberlechner and
• Ronald Micura

Beilstein J. Org. Chem. 2022, 18, 1617–1624, doi:10.3762/bjoc.18.172

• , glycogen synthase kinase 3 (GSK-3), leucine-rich repeat kinase 2 (LRRK2), tyrosine phosphorylation-regulated kinase-1A (DYRK1A) and CDC2-like kinase 1 (CLK1), and fatty acid amide hydrolase (FAAH) [4]). Similar properties were ascertained for 1-deazapurine derivatives (imidazo[4,5-b]pyridines) and

Synthesis of C6-modified mannose 1-phosphates and evaluation of derived sugar nucleotides against GDP-mannose dehydrogenase

• Sanaz Ahmadipour,
• Alice J. C. Wahart,
• Jonathan P. Dolan,
• Laura Beswick,
• Chris S. Hawes,
• Robert A. Field and
• Gavin J. Miller

Beilstein J. Org. Chem. 2022, 18, 1379–1384, doi:10.3762/bjoc.18.142

• MacDonald phosphorylation [9]. Details of this synthesis were reported by us previously [10]. In this work, we attempted to use these optimised MacDonald conditions to directly access 17 from 14, but the reaction exhibited extensive degradation upon multiple attempts. Instead we started from 14 and

• completed a selective anomeric deacetylation on a gram-scale using ammonium acetate in DMF, to afford hemi-acetal 15 in good yield (80%) [11]. This was followed by phosphorylation of the anomeric position using diphenylphosphoryl chloride as the phosphorous electrophile, following deprotonation of 15 using

Make or break: the thermodynamic equilibrium of polyphosphate kinase-catalysed reactions

• Michael Keppler,
• Sandra Moser,
• Henning J. Jessen,
• Christoph Held and
• Jennifer N. Andexer

Beilstein J. Org. Chem. 2022, 18, 1278–1288, doi:10.3762/bjoc.18.134

• preferences, as most enzymes catalyse all phosphorylation steps during extended reaction times; also higher phosphorylated species have been detected in the reactions [7][8]. The enzymes characterised from E. coli (EcPPK1) and Sinorhizobium meliloti (renamed Ensifer meliloti, SmPPK2) are often regarded as

• optimisation of biocatalytic syntheses of nucleotides as well as nucleotide regeneration systems (Figure 3a and 3b). In a regeneration system (exemplarily shown for the hexokinase-catalysed phosphorylation of glucose (Figure 3a) the formed ADP has to be converted back to ATP to maintain a sufficient pool of

• can be embedded in complex biosynthetic networks such as in vitro S-adenosylmethionine (SAM)- or carbon dioxide fixation cycles, and de novo nucleobase synthesis [38][39][40][41]. For the biocatalytic synthesis of ATP or derivatives, up to three consecutive phosphorylation reactions are coupled in a

Lewis acid-catalyzed Pudovik reaction–phospha-Brook rearrangement sequence to access phosphoric esters

• Jin Yang,
• Dang-Wei Qian and
• Shang-Dong Yang

Beilstein J. Org. Chem. 2022, 18, 1188–1194, doi:10.3762/bjoc.18.123

• ][6][7][8][9]. Therefore, many efficient methods have been developed in the past decades to synthesize different types of phosphoric esters [10][11][12][13][14][15][16][17][18]. Traditional methods for the construction of P−O bonds in phosphoric esters rely on the phosphorylation of alcohols or phenol

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

• , their enzymatic basis has remained elusive except for the exo-olefin formation in valanimycin biosynthesis, which is mediated by the phosphorylation of a serine moiety by VlmJ and the subsequent dehydration by VlmK [33]. To obtain insights into the late-stage diversification mechanisms, we focused on

Efficient production of clerodane and ent-kaurane diterpenes through truncated artificial pathways in Escherichia coli

• Fang-Ru Li,
• Xiaoxu Lin,
• Qian Yang,
• Ning-Hua Tan and
• Liao-Bin Dong

Beilstein J. Org. Chem. 2022, 18, 881–888, doi:10.3762/bjoc.18.89

• to reinforce the supply of IPP and DMAPP via two sequential phosphorylation reactions. Optimization of these constructs provided terpentetriene and ent-kaurene titers of 66 ± 4 mg/L and 113 ± 7 mg/L, respectively, in shake-flask fermentation. The truncated pathways to overproduce clerodane and ent

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

• microorganisms to more complex beings, such as higher plants and animals [1]. Actually, quinones play important roles in several physiological processes in these organisms, such as photosynthesis [2] and oxidative phosphorylation [3][4], as well as many other metabolic processes [5][6][7]. Quinones also received

• , 68), giving the pegylated product and N-hydroxysuccinimide (NHS) as the sole byproduct. The latter can be recycled again to the pegylation reagent. This study showed better results when compared to the methodology for a phosphorylation of 14 developed by Fieser [119], a procedure carried out in two

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

• cytotoxicity, respectively. Capping the N-terminus with a Boc-protecting group (9) or a guanidinoacetic acid motif (10a and 10b) renders the molecules with higher cytotoxicity (resulting in cell viabilities of about 70%) than those of 2f and 2g. Compounds without phosphorylation (11a, 11b and 12a–c) show

1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis

• Ruan Carlos B. Ribeiro,
• Patricia G. Ferreira,
• Amanda de A. Borges,
• Luana da S. M. Forezi,
• Fernando de Carvalho da Silva and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 53–69, doi:10.3762/bjoc.18.5

• oxidative processes in aerobic metabolism, photosynthesis, oxidative phosphorylation, blood clotting, and other electron transport reactions [7][8]. These biochemical functions give them several biological activities, such as antibacterial, fungicidal, antimalarial, trypanocidal, and antitumor. For this

Synthetic strategies toward 1,3-oxathiolane nucleoside analogues

• Umesh P. Aher,
• Dhananjai Srivastava,
• Girij P. Singh and
• Jayashree B. S

Beilstein J. Org. Chem. 2021, 17, 2680–2715, doi:10.3762/bjoc.17.182

• counterparts during DNA or RNA synthesis, a biological role that is crucial for cellular reproduction [2]. Most of the drugs that are incorporated in the viral DNA upon phosphorylation in vivo block the DNA polymerase enzyme. However, DNA polymerase recognizes 2’,3’-dideoxynucleosides as substrates, which are

• as zidovudine, didanosine, zalcitabine, stavudine, lamivudine (1), and abacavir (a carbanucleoside) for treating HIV infection, along with protease and nonnucleoside reverse transcriptase inhibitors (NNRTIs). Phosphorylation of 1,3-oxathiolane nucleosides, such as 3TC (1) and FTC (2), occurs in vivo

• ), which may be responsible for such differences [24]. Initial results point at a conventional mechanism of action. Therein, the investigation of the cellular metabolism predicts triphosphate formation of the compounds by phosphorylation, and the resulting nucleotide is a selective inhibitor of the HIV-1

(Phenylamino)pyrimidine-1,2,3-triazole derivatives as analogs of imatinib: searching for novel compounds against chronic myeloid leukemia

• Luiz Claudio Ferreira Pimentel,
• Lucas Villas Boas Hoelz,
• Henayle Fernandes Canzian,
• Frederico Silva Castelo Branco,
• Andressa Paula de Oliveira,
• Vinicius Rangel Campos,
• Floriano Paes Silva Júnior,
• Rafael Ferreira Dantas,
• Jackson Antônio Lamounier Camargos Resende,
• Anna Claudia Cunha,
• Nubia Boechat and
• Mônica Macedo Bastos

Beilstein J. Org. Chem. 2021, 17, 2260–2269, doi:10.3762/bjoc.17.144

• TKIs that are even more potent than IMT, such as nilotinib [6][7]. These drugs act as inhibitors at the ATP binding site in the inactive form of BCR-Abl-1, preventing the binding of the protein to ATP in a competitive manner and resulting in the interruption of the substrate phosphorylation process and

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

• acetylation, methylation, and phosphorylation, which alter TF access; and iii) methylation of CpG islands in promoter regions that inhibit gene expression [4][5]. There are currently several isolated studies of TF–glycogene interactions, but a systematic “systems-level analysis” is absent. Many of these

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

• modification of monosaccharides, for example through sulfation, acetylation or phosphorylation, which follow the same pattern as decoration. Glycologue structure identifiers order branches by linkage position, writing the branch with the lowest linkage first, reading from right to left. Modifiers are written