Computational design for enantioselective CO₂ capture: asymmetric frustrated Lewis pairs in epoxide transformations

• Maxime Ferrer,
• Iñigo Iribarren,
• Tim Renningholtz,
• Ibon Alkorta and
• Cristina Trujillo

Beilstein J. Org. Chem. 2024, 20, 2668–2681, doi:10.3762/bjoc.20.224

• performance, for example, the reaction rate, is displayed as a function of the catalyst–substrate interaction, for example, the adsorption energy when considering a heterogeneous catalyst (Figure 1A). The resulting plot exhibits a volcano-like shape consisting of at least two slopes with the best-performing

• determines a function such as E1 = f(E2, TS3). The quality of these correlations is assessed through the square of the Pearson coefficient. The pair of stationary points has to correlate with the energies of the six stationary points previously presented. The quality of the pair considered to describe well

The scent gland composition of the Mangshan pit viper, Protobothrops mangshanensis

• Jonas Holste,
• Paul Weldon,
• Donald Boyer and
• Stefan Schulz

Beilstein J. Org. Chem. 2024, 20, 2644–2654, doi:10.3762/bjoc.20.222

• -hexadecylglycerol, as well as other common long-chain alcohols and amides. Although a general defensive function has been proposed for snake abdominal scent glands, the specific chemistry and moderate amounts of acids reported here may suggest a function in chemical signaling for the Mangshan pit viper. In addition

• common fatty acids, which allow for easier evaporation, make acids A–F suitable to be used in chemical communication of P. mangshanensis. However, actual proof of function can only be obtained by bioassays with synthetic material. Interestingly, there are a few structurally related compounds in the

• of several microderivatizations and finally confirmed structurally by synthesis. The structural uniqueness of the compounds, not found in other snake species, suggests a function, may it be in chemical communication, defense, or other traits. The other scent gland constituents are commonly found in

Deciphering the mechanism of γ-cyclodextrin’s hydrophobic cavity hydration: an integrated experimental and theoretical study

• Stiliyana Pereva,
• Stefan Dobrev,
• Tsveta Sarafska,
• Valya Nikolova,
• Silvia Angelova,
• Tony Spassov and
• Todor Dudev

Beilstein J. Org. Chem. 2024, 20, 2635–2643, doi:10.3762/bjoc.20.221

• is described in the first two papers in the series on the hydration of α-CD and β-CD, respectively [13][14]. The performed M062X/6-31G(d,p) frequency calculations for each structure ascertain that the wave function corresponds to a minimum on a potential energy hypersurface, but also yields the

Applications of microscopy and small angle scattering techniques for the characterisation of supramolecular gels

• Connor R. M. MacDonald and
• Emily R. Draper

Beilstein J. Org. Chem. 2024, 20, 2608–2634, doi:10.3762/bjoc.20.220

• result of a photon or neutron of wavelength (λ) scattering off the sample at an angle of 2φ (Equation 1 and Figure 12). Typically, a 2D detector measures the scattered radiation to determine the scattering intensity (I(q)) and is measured as a function of q. The scattering vector has units of reciprocal

Efficient modification of peroxydisulfate oxidation reactions of nitrogen-containing heterocycles 6-methyluracil and pyridine

• Alfiya R. Gimadieva,
• Yuliya Z. Khazimullina,
• Aigiza A. Gilimkhanova and
• Akhat G. Mustafin

Beilstein J. Org. Chem. 2024, 20, 2599–2607, doi:10.3762/bjoc.20.219

• are widely used in pharmacology due to their pronounced biological activities and low toxicities. The introduction of a hydroxy function into uracil and pyridine molecules has led to compounds with antioxidant, anti-inflammatory, and immunomodulatory activity (3-hydroxy-6-methyl-2-ethylpyridine, 5

• : oxidation; 6-methyluracil; peroxydisulfate; phthalocyanine catalysts; pyridine; Introduction The Elbs and Boyland–Sims peroxydisulfate oxidation reactions offer a convenient means of introducing the hydroxy function into phenols and aromatic amines [1]. The oxidation of phenol using peroxydisulfate was

Machine learning-guided strategies for reaction conditions design and optimization

• Lung-Yi Chen and
• Yi-Pei Li

Beilstein J. Org. Chem. 2024, 20, 2476–2492, doi:10.3762/bjoc.20.212

• nodes and edges through recursive message passing and a readout function, resulting in a molecular representation. There are many variants of GNN models [140][141][142][143], most of which are based on the message passing neural network (MPNN) framework proposed by Gilmer et al. [144]. Encoding

• mapping (AAM) is a process that establishes the correspondence between atoms before and after a reaction, reflecting the reaction mechanism. AAM-exempted methods [145][146][147][148][149][150] apply graph convolutions to each reactant and product molecule separately, and then use a pooling function or

HFIP as a versatile solvent in resorcin[n]arene synthesis

• Hormoz Khosravi,
• Valeria Stevens and
• Raúl Hernández Sánchez

Beilstein J. Org. Chem. 2024, 20, 2469–2475, doi:10.3762/bjoc.20.211

• unique bowl-shape structures and self-assembly in solution have facilitated their widespread use as building blocks in nanomaterials [61][62]. Nevertheless, precisely due to their vast number of applications, functionalized resorcin[n]arenes are needed that meet the needs of the desired function. For

Homogeneous continuous flow nitration of O-methylisouronium sulfate and its optimization by kinetic modeling

• Jiapeng Guo,
• Weike Su and
• An Su

Beilstein J. Org. Chem. 2024, 20, 2408–2420, doi:10.3762/bjoc.20.205

• . Determining the apparent reaction kinetics The variation in the conversion of IO (xIO) as the function of time (t) at different temperatures (30 °C, 35 °C, 40 °C) and H2SO4 mass fractions (88%, 90%, 92%, 94%, 96%, and 98%) is depicted in Figure S3 in Supporting Information File 1 and subsequently modeled

• type of compound, and Mc is the activity coefficient function introduced in the next section. By shifting the terms in Equation 9, Equation 10 can be obtained as: Therefore, by plotting as the vertical coordinate and Mc as the horizontal coordinate, the values of n and k0 can be obtained from the

• , specifically when the H2SO4 concentrations were between 15.2 and 18.4 mol/L. By fitting the predicted data, Mc as a function of the H2SO4 concentration at a given temperature was determined (Figure S4 in Supporting Information File 1). In addition, the values of Mc for different sulfuric acid concentrations at

Asymmetric organocatalytic synthesis of chiral homoallylic amines

• Nikolay S. Kondratyev and
• Andrei V. Malkov

Beilstein J. Org. Chem. 2024, 20, 2349–2377, doi:10.3762/bjoc.20.201

• , creating the desired syn-(2R,3S)-homoallylic amine 120 in high diastereo- and enantioselectivity. The reaction was tested with various aryl, benzyl, allyl, and alkyl-functionalised β-formyl N-morpholinyl amides 119; the amide function was also varied. Yields were scattered across the 31–90% range, with the

Improved deconvolution of natural products’ protein targets using diagnostic ions from chemical proteomics linkers

• Andreas Wiest and
• Pavel Kielkowski

Beilstein J. Org. Chem. 2024, 20, 2323–2341, doi:10.3762/bjoc.20.199

• conjugate(s) and the desired analytical output with the information about the protein and conjugate identity. Thus, the linkers have not only the function to simply connect the probe scaffold with an affinity or reporter tag, but they carry previously underappreciated features enhancing the capabilities of

Hydrogen-bond activation enables aziridination of unactivated olefins with simple iminoiodinanes

• Phong Thai,
• Lauv Patel,
• Diyasha Manna and
• David C. Powers

Beilstein J. Org. Chem. 2024, 20, 2305–2312, doi:10.3762/bjoc.20.197

• ]. Iminoiodinanes (ArI=NR) are a subclass of hypervalent iodine reagents that function as nitrene equivalents in synthesis [5][6]. The direct reaction of iminoiodinanes with olefins, which could be envisioned to give rise to aziridines directly, is typically not observed and thus families of transition metal

Catalysing (organo-)catalysis: Trends in the application of machine learning to enantioselective organocatalysis

• Stefan P. Schmid,
• Leon Schlosser,
• Frank Glorius and
• Kjell Jorner

Beilstein J. Org. Chem. 2024, 20, 2280–2304, doi:10.3762/bjoc.20.196

• ]. While the accuracy of the model is paramount, interpretability is also highly desirable. In this regard, MLR bears the advantage that it yields a directly interpretable function which can be used for mechanistic inference. However, it is important to note that the caveat of correlation and causality

• their OSCAR [31] database, the authors used the NaviCatGA genetic algorithm [118] to find the most general catalysts. The fitness function comprised multiple objectives, including the median of the enantioselectivity and activity across the generality probing set. The usage of a multi-objective

Cell-free protein synthesis with technical additives – expanding the parameter space of in vitro gene expression

• Tabea Bartsch,
• Stephan Lütz and
• Katrin Rosenthal

Beilstein J. Org. Chem. 2024, 20, 2242–2253, doi:10.3762/bjoc.20.192

• of the intracellular environment on the function and cellular behavior of proteins are composition, viscosity, and macromolecular crowding [16], these parameters could have a strong impact on the protein synthesis performance using CFPS. For example, the addition of chemical chaperones, such as

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

• physical functions [3]. Glycoscience encompasses the comprehensive study of glycans focusing on their structural, biosynthetic, biological and evolutionary aspects [4], thus playing a central role in the identification and characterisation of the glycome’ structure and function, and in unveiling its

• of chemical processes [20][21], transporting and storing molecules [22], transducing and integrating information [23] providing structural and mechanical support [24], and generating movement [25], among other functions [26]. To fold and carry out their function properly, proteins often need post

• simulations, it is fundamental not only to build their 3D structure but also to choose the appropriate force field, that is a set of empirical energy functions and parameters used to calculate the potential energy of a system as a function of the molecular coordinates. The collection of equations and

Diastereoselective synthesis of highly substituted cyclohexanones and tetrahydrochromene-4-ones via conjugate addition of curcumins to arylidenemalonates

• Deepa Nair,
• Abhishek Tiwari,
• Banamali Laha and
• Irishi N. N. Namboothiri

Beilstein J. Org. Chem. 2024, 20, 2016–2023, doi:10.3762/bjoc.20.177

• properties such as anticancer, anti-HIV protease, anti-ageing, anti-inflammatory and anti-oxidant, to name a few [12][13][14][15][16][17][18][19][20][21][22][23]. Considering the fact that curcumin’s uniqueness is associated with its ability to function as a multifunctional substrate in various organic

Understanding X-ray-induced isomerisation in photoswitchable surfactant assemblies

• Beatrice E. Jones,
• Camille Blayo,
• Jake L. Greenfield,
• Matthew J. Fuchter,
• Nathan Cowieson and
• Rachel C. Evans

Beilstein J. Org. Chem. 2024, 20, 2005–2015, doi:10.3762/bjoc.20.176

• irradiation to form the Z-rich PSS and addition of excess hydrobromic acid as a function of time held in the dark. The grey lines indicate time intervals of (a) 3 minutes and (b) 1 hour. Effect of X-ray exposure time on high-concentration samples of AAPTAB in water, (a) 10 wt % and (b) 90 wt %, after ex-situ

Negishi-coupling-enabled synthesis of α-heteroaryl-α-amino acid building blocks for DNA-encoded chemical library applications

• Matteo Gasparetto,
• Balázs Fődi and
• Gellért Sipos

Beilstein J. Org. Chem. 2024, 20, 1922–1932, doi:10.3762/bjoc.20.168

• crucial function in many biological processes. Due to their bifunctional character, they have been also used for combinatorial chemistry purposes, such as the preparation of DNA-encoded chemical libraries. We developed a practical synthesis for α-heteroaryl-α-amino acids starting from an array of small

• , while also holding a crucial function in many biological processes [8]. Non-canonical amino acids (NCAs) are widely used in medicinal chemistry [9]. Not surprisingly, they also find broad use as bifunctional building blocks (BBs) for DELs. In an early example, an 800-million-members DEL utilized Fmoc

The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

• . Sashidhara et al. reported no conversion, while Liu et al. reported a 58% yield of the GBB product, postulating the ability of ethylene glycol to function as an activator (through hydrogen bonding) and a facilitator of proton transfer. After this discovery, ethylene glycol has never been employed in GBB

Hetero-polycyclic aromatic systems: A data-driven investigation of structure–property relationships

• Sabyasachi Chakraborty,
• Eduardo Mayo Yanes and
• Renana Gershoni-Poranne

Beilstein J. Org. Chem. 2024, 20, 1817–1830, doi:10.3762/bjoc.20.160

• properties as a function of the number of building blocks of each type (from 1–4; the number of examples containing more than 4 building blocks of a single type are too few to be statistically meaningful). Not surprisingly, the trends shown in Figure 10 reiterate and further substantiate some of the previous

Discovery of antimicrobial peptides clostrisin and cellulosin from Clostridium: insights into their structures, co-localized biosynthetic gene clusters, and antibiotic activity

• Moisés Alejandro Alejo Hernandez,
• Katia Pamela Villavicencio Sánchez,
• Rosendo Sánchez Morales,
• Karla Georgina Hernández-Magro Gil,
• David Silverio Moreno-Gutiérrez,
• Eddie Guillermo Sanchez-Rueda,
• Yanet Teresa-Cruz,
• Brian Choi,
• Armando Hernández Garcia,
• Alba Romero-Rodríguez,
• Oscar Juárez,
• Siseth Martínez-Caballero,
• Mario Figueroa and
• Corina-Diana Ceapă

Beilstein J. Org. Chem. 2024, 20, 1800–1816, doi:10.3762/bjoc.20.159

• function–structure relationships and how they impact biological activity. Since we have not found evidence of horizontal transfer of the cloA1 and cloA2 gene clusters, it is an interesting speculation that they could constitute the origin of this family and that, by duplicating one of these clusters, C

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

• epoxide was then opened by treatment with sodium azide and boric acid, yielding the azide derivative 146 in 87% from estrone. A subsequent reduction of the azide with LiAlH4 provided the aminoalcohol derivative 147 in 64% yield. Then, a chloroacetamido moiety was formed at the amino function in 51% yield

Chemo-enzymatic total synthesis: current approaches toward the integration of chemical and enzymatic transformations

• Ryo Tanifuji and
• Hiroki Oguri

Beilstein J. Org. Chem. 2024, 20, 1693–1712, doi:10.3762/bjoc.20.151

• substrate–enzyme combinations. The integrative approach of combining intriguing enzymes in ever-evolving biosynthetic research with chemical synthesis, would foster collaborative breakthroughs in the interdisciplinary landscape of natural product biosynthesis, total synthesis as well as function- and

A fiber-optic spectroscopic setup for isomerization quantum yield determination

• Anouk Volker,
• Jorn D. Steen and
• Stefano Crespi

Beilstein J. Org. Chem. 2024, 20, 1684–1692, doi:10.3762/bjoc.20.150

• different python scripts (provided in Supporting Information File 1). The rate equations are ordinary differential equations (ODEs) and can thus be solved numerically using existing methods in the SciPy package [50]. An absorbance function was constructed, which takes the solution of the ODEs to model the

• absorbance over time. This absorbance function was then fitted to the measured absorbance at the wavelength of irradiation (or wavelengths, for a non-monochromatic excitation light). The parameters ΦA→B and ΦB→A were evaluated to minimize the residual sum of squares (RSS) between the measured and fitted

Methyltransferases from RiPP pathways: shaping the landscape of natural product chemistry

• Maria-Paula Schröder,
• Isabel P.-M. Pfeiffer and
• Silja Mordhorst

Beilstein J. Org. Chem. 2024, 20, 1652–1670, doi:10.3762/bjoc.20.147

• peptides at the C-terminal carboxy group of different amino acids, namely methionine, isoleucine, and valine. This demonstrates its tolerance to various substrates. LahSB does not require the leader peptide or other modifying enzymes to carry out its function [72], making it a promising tool for

• biocatalytic applications. The co-crystallisation of LahSB with bound SAH provides important details about the structure–function relationship, the substrate–enzyme interaction, and the cofactor binding site (Figure 5). This structural information, including the residues involved in binding, is essential for

• enzyme engineering and rational design [73][74]. Lentzea kentuckyensis sp. produces lassomycin (Figure 4), a lasso peptide, with a methyl ester at the C-terminus. The las cluster encodes LasF, which is predicted to function as an O-MT. Since no other putative MT is encoded in the las cluster, LasF is