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

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

• progressive conversion of the starting material into the C6-derivative 64 (Scheme 18). Chen et al. reported the synthesis of C2-phosphorylated indoles via 1,2-phosphorylation of 3-indolylmethanols with H-phosphine oxides or H-phosphonates under Brønsted acid activation [72]. The scope of the reaction includes

Annulation of a 1,3-dithiole ring to a sterically hindered o-quinone core. Novel ditopic redox-active ligands

• Sergey V. Norkov,
• Anton V. Cherkasov,
• Andrey S. Shavyrin,
• Maxim V. Arsenyev,
• Viacheslav A. Kuropatov and
• Vladimir K. Cherkasov

Beilstein J. Org. Chem. 2021, 17, 273–282, doi:10.3762/bjoc.17.26

• Information File 1). Taking into account the selectivity and almost quantitative yield of this reaction, such a phosphorylation seems to be useful for the protection of the dioxolene site in case of necessity to modify the periphery of the molecule. The thiocarbonyl group in 6a also remained unchanged upon

Silver-catalyzed synthesis of β-fluorovinylphosphonates by phosphonofluorination of aromatic alkynes

• Yajing Zhang,
• Qingshan Tian,
• Guozhu Zhang and
• Dayong Zhang

Beilstein J. Org. Chem. 2020, 16, 3086–3092, doi:10.3762/bjoc.16.258

• . Among the strategies for constructing diverse alkenes containing two-heteroatom bonds, such as disulfonylation [14][15][16], heterohalogenation [17][18][19][20], bis(trifluoromethyl)thiolation [21], and phosphorylation [22], the direct heterodifunctionalization of alkynes using three-component reactions

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

• possible modification site. For example, “A$GN” represents a GlcNAc connected to a galactose that might be modified. The modification can be specified (e.g., phosphorylation on the 2nd carbon) in the typical way, with square brackets “A$[2P]GN”. Recommendation 9 – “Branching index.” In LiCoRR we have

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

• of magnesium ions on metabolic transformations of nucleosides [45], in particular on the phosphorylation of the primary hydroxy group of pentoses, catalyzed by ribokinases [46], as well as on the cascade synthesis of nucleosides starting from pentoses [47][48][49][50] has been described. Based on the

Synthesis of monophosphorylated lipid A precursors using 2-naphthylmethyl ether as a protecting group

• Jundi Xue,
• Ziyi Han,
• Gen Li,
• Khalisha A. Emmanuel,
• Cynthia L. McManus,
• Qiang Sui,
• Dongmian Ge,
• Qi Gao and
• Li Cai

Beilstein J. Org. Chem. 2020, 16, 1955–1962, doi:10.3762/bjoc.16.162

• -antigen [2]. While O-antigen and the core oligosaccharide are exposed to the external environment, lipid A, the hydrophobic domain of LPS, is embedded in the cell wall. The lipid A substructure is relatively conserved that consists of a β-1,6-linked diglucosamine with 1,4′-di-O-phosphorylation and 2,2′-N

• might harness these immunostimulatory effects are particularly valuable as they can provide basis for the development of vaccines and adjuvants. For example, recent studies have disclosed that both the fatty acid structure and the phosphorylation degree can affect the activity and endotoxic effects [7

• , followed by deprotection, acylation, and phosphorylation reactions (Scheme 4). The triflic acid (TfOH)-mediated glycosylation of donor 20 and acceptor 18 in the presence of molecular sieves in CH2Cl2 at −20 °C gave disaccharide 24 [14] in excellent yield (β-anomer only). The N’-Troc protecting group (non

Selective preparation of tetrasubstituted fluoroalkenes by fluorine-directed oxetane ring-opening reactions

• Clément Q. Fontenelle,
• Thibault Thierry,
• Romain Laporte,
• Emmanuel Pfund and
• Thierry Lequeux

Beilstein J. Org. Chem. 2020, 16, 1936–1946, doi:10.3762/bjoc.16.160

• VIII was observed due to the difficulty of phosphorylation of the substrate by kinases [16]. The first kinase phosphorylation step is generally rate limiting, and the prior introduction of a phosphate or phosphonate function can circumvent this problem. The preparation of diols VIII was realized by

Synthesis, docking study and biological evaluation of ᴅ-fructofuranosyl and ᴅ-tagatofuranosyl sulfones as potential inhibitors of the mycobacterial galactan synthesis targeting the galactofuranosyltransferase GlfT2

• Marek Baráth,
• Jana Jakubčinová,
• Zuzana Konyariková,
• Stanislav Kozmon,
• Katarína Mikušová and
• Maroš Bella

Beilstein J. Org. Chem. 2020, 16, 1853–1862, doi:10.3762/bjoc.16.152

• investigations on their more stable analogs resulted in the synthesis of stable 1-O-phoshono-β-ᴅ-psicofuranosyl sulfone, which was prepared by a simultaneous phosphorylation and oxidation of ethyl 2-thio-β-ᴅ-psicofuranoside with dibenzyl N,N-dimethylphosphoramidite catalyzed by 1H-tetrazole and followed by

• complex structure and also mimic its partial charges and charge distribution. Herein, the molecular docking, synthesis and inhibitory activity of ᴅ-fructofuranosyl and ᴅ-tagatofuranosyl sulfones 1–3 against GlfT2 are discussed. Moreover, we extended the scope of the simultaneous phosphorylation and

• -chloroperbenzoic acid (m-CPBA, 12 equiv) led to the simultaneous phosphorylation of the hydroxy group and to the oxidation of the sulfide to give 1-O-dibenzyloxyphosphoryl-ᴅ-fructofuranosyl sulfones 7α, 8α, 8β and 9α in excellent yields (Scheme 1). Final removal of benzyl protecting groups by catalytic

Synthesis of Streptococcus pneumoniae serotype 9V oligosaccharide antigens

• Sharavathi G. Parameswarappa,
• Claney L. Pereira and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2020, 16, 1693–1699, doi:10.3762/bjoc.16.140

• escape the host immune response [1][7]. These polysaccharides of SP consist of repeating units (RU) that range from di- to heptasaccharides that may be branched and/or charged [8]. Modifications such as O-acetylation, phosphorylation, and sulfation further increase CPS complexity. Many bacterial