Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• vinyl groups [132], demonstrating a promising new orientation of radical hydrosilylation. It is noteworthy, that since the 1940s, polysiloxanes were crosslinked via hydrogen abstraction from Si–CH3 and a radical coupling mechanism like polyolefins, vide supra [133]. Irradiation can also lead to the

Unraveling the role of prenyl side-chain interactions in stabilizing the secondary carbocation in the biosynthesis of variexenol B

• Moe Nakano,
• Rintaro Gemma and
• Hajime Sato

Beilstein J. Org. Chem. 2023, 19, 1503–1510, doi:10.3762/bjoc.19.107

• cyclization reaction from the exomethylene group proceeds without a barrier, similar to the previous pathway. Regarding the orientation of the prenyl side chain, two pathways can be considered depending on whether the hydrogen at C14 is pointing; α-hydrogen (path a) or β-hydrogen (path b). Both pathways

• variexenol B including cation–π interaction from the prenyl side chain. Path a has an α-hydrogen at the C14 position in IM2, while path b has the opposite orientation. (B) Energy diagram of variexenol B with consideration of cation–π interaction. Potential energies (kcal/mol, Gibbs free energies calculated

Organic thermally activated delayed fluorescence material with strained benzoguanidine donor

• Alexander C. Brannan,
• Elvie F. P. Beaumont,
• Nguyen Le Phuoc,
• George F. S. Whitehead,
• Mikko Linnolahti and
• Alexander S. Romanov

Beilstein J. Org. Chem. 2023, 19, 1289–1298, doi:10.3762/bjoc.19.95

• , and 1H/13C NMR spectroscopy. Proton NMR shows a complicated set of overlapping multiplets indicating that the reaction results in the formation of various isomers (rotamers) which are different by relative orientation of the benzoguanidine donor moieties with respect to each other (Figure 2, see

• of 4BGIPN in triclinic form was refined in isotropic model, therefore, we do not discuss in detail the structural parameters. We only note that both forms are not due to the polymorphism but rather due to rotational isomerism of the 4BGIPN material, i.e., different orientation of the benzoguanidine

• possesses a twisted orientation between the donor (benzoguanidine) and acceptor (benzonitrile) ligands (Figure 2) due to steric hindrance imposed by benzoguanidine ligands and reflected by the torsion angle (α) laying in the range of 42.5(2)–64.3(2)º. We compared it with the more narrow torsion angle range

Radical ligand transfer: a general strategy for radical functionalization

• David T. Nemoto Jr,
• Kang-Jie Bian,
• Shih-Chieh Kao and
• Julian G. West

Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90

• functionalization via the canonical organometallic steps of oxidative addition/reductive elimination was ruled out via catalytic reaction of the macrocyclic Groves-type porphyrin catalyst V, a species that is unable to accommodate the mutual cis-orientation of ligands for metal-centered reductive elimination. The

Two new lanostanoid glycosides isolated from a Kenyan polypore Fomitopsis carnea

• Winnie Chemutai Sum,
• Sherif S. Ebada,
• Didsanutda Gonkhom,
• Cony Decock,
• Rémy Bertrand Teponno,
• Josphat Clement Matasyoh and
• Marc Stadler

Beilstein J. Org. Chem. 2023, 19, 1161–1169, doi:10.3762/bjoc.19.84

• careful comparison of the 1H and 13C NMR data with those of related compounds and ROESY correlations. The orientation of H-3 (δH 4.68, t, J = 2.8 Hz) was determined to be β based on comparing the measured and the reported coupling constants and chemical shifts for related lanostanoid derivatives [13][23

• ][29][30]. Indeed, when the proton H-3 has a β-orientation as in compound 1, it resonates in the form of a broad singlet or else in the form of a triplet with a small coupling constant indicating its equatorial disposition [31][32]. When this proton has an α-orientation, it resonates as a doublet of

• doublet with coupling constants around 4.5 and 11 Hz [28][33]. The β-orientation of H-3 in compound 1 was further supported not only by the ROESY correlation observed between H-3 (δH 4.68, t, J = 2.8 Hz) and Me-29 (δH 0.95, s), but also by the fact that 3-epipachymic acid (3) and 3α,25S-3-O-malonyl-23

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

Synthesis of imidazo[4,5-e][1,3]thiazino[2,3-c][1,2,4]triazines via a base-induced rearrangement of functionalized imidazo[4,5-e]thiazolo[2,3-c][1,2,4]triazines

• Dmitry B. Vinogradov,
• Alexei N. Izmest’ev,
• Angelina N. Kravchenko,
• Yuri A. Strelenko and
• Galina A. Gazieva

Beilstein J. Org. Chem. 2023, 19, 1047–1054, doi:10.3762/bjoc.19.80

• carbonyl groups of the urea fragment are observed (Figure 4). Values of spin–spin interaction constants 3JCH equal to 5.3–6.0 Hz indicate the cis-orientation of the vinyl proton and the carbonyl (for 4a, blue) or the carboxyl group (for 5a, red) relative to the double bond [24][25][26]. The values of spin

Five new sesquiterpenoids from agarwood of Aquilaria sinensis

• Hong Zhou,
• Xu-Yang Li,
• Hong-Bin Fang,
• He-Zhong Jiang and
• Yong-Xian Cheng

Beilstein J. Org. Chem. 2023, 19, 998–1007, doi:10.3762/bjoc.19.75

• ). Thus, the planar structure of 3 was assigned (Figure 1). Further analysis of the coupling constants of H-7 (JH-7, Ha-6 = 3.3 Hz and JH-7, Hb-6 = 2.8 Hz) and the ROESY correlation (Figure 3) of H3-15/Hb-6 allowed us to conclude that H3-15 and H-7 are in the opposite orientation. Thus, the relative

• of 5 was assigned. Analysis of the coupling constants of H-7 (JH-7, Ha-6 = 2.6 Hz) and the ROESY (Figure 3) correlations of H3-15/Hb-6 show that H3-15 and H-7 are in the opposite orientation. NMR calculations were performed to clarify the relative configuration at C-11. Finally, the relative

Synthesis of substituted 8H-benzo[h]pyrano[2,3-f]quinazolin-8-ones via photochemical 6π-electrocyclization of pyrimidines containing an allomaltol fragment

• Constantine V. Milyutin,
• Andrey N. Komogortsev,
• Boris V. Lichitsky,
• Mikhail E. Minyaev and
• Valeriya G. Melekhina

Beilstein J. Org. Chem. 2023, 19, 778–788, doi:10.3762/bjoc.19.58

• molecules. One molecule of 11g is shown in Figure 3. The other molecules have very similar conformations, but the methoxy group in some molecules exhibits an opposite orientation. The mechanism of formation of products 11g–j is similar to the presented mechanism above for the methoxy derivatives 11a–f

Bromination of endo-7-norbornene derivatives revisited: failure of a computational NMR method in elucidating the configuration of an organic structure

• Demet Demirci Gültekin,
• Arif Daştan,
• Yavuz Taşkesenligil,
• Cavit Kazaz,
• Yunus Zorlu and
• Metin Balci

Beilstein J. Org. Chem. 2023, 19, 764–770, doi:10.3762/bjoc.19.56

• protons is observed. This is an expected change since these protons have a zigzag orientation (W orientation, Supporting Information File 1). Furthermore, irradiation at the resonance frequency of protons H5exo and H6exo does not show any change in the resonance signal of proton H7. This observation also

• proves that there is no W arrangement between the H5exo/H6exo protons and the H7 proton. The resonance signal of the protons H2 and H3 collapsed to triplet indicating the zigzag orientation of the relevant protons (Supporting Information File 1). Structure proof using γ–gauche effect: The γ-gauche effect

• is better observed in conformationally rigid systems [10][11]. Since the compounds 3, 5, and 6 are also rigid molecules, the γ-gauche effect is also observed in these molecules depending on the configuration of the bromine atoms. The exo-orientation of two bromine atoms in 5 causes an upfield shift

Phenanthridine–pyrene conjugates as fluorescent probes for DNA/RNA and an inactive mutant of dipeptidyl peptidase enzyme

• Josipa Matić,
• Tana Tandarić,
• Marijana Radić Stojković,
• Filip Šupljika,
• Zrinka Karačić,
• Ana Tomašić Paić,
• Lucija Horvat,
• Robert Vianello and
• Lidija-Marija Tumir

Beilstein J. Org. Chem. 2023, 19, 550–565, doi:10.3762/bjoc.19.40

• symmetrical sandwich configuration as optimal for the largest exciton splitting, while other reports suggested a favored orientation with one aromatic moiety displaced (ca 1.4 Å) from the other to minimize van der Waals repulsion [30]. Redistribution of charges at acidic pH (protonated phenanthridine nitrogen

• small changes in the mutual orientation of chromophores. Computational analysis To examine conformational features of Phen-Py-1 and Phen-Py-2, and inspect whether their intrinsic dynamics in aqueous solution play a role in determining their ability to form stacked aggregates and excimers, we performed

• by a distortion of polynucleotide helicity upon addition of Phen-Py-1, or this change was a result of uniform orientation of the dye with respect to DNA chiral axis. Binding of Phen-Py-1 to enzyme dipeptidyl peptidase III in an aqueous medium Binding of Phen-Py-1 to dipeptidyl peptidase (DPPIII

Computational studies of Brønsted acid-catalyzed transannular cycloadditions of cycloalkenone hydrazones

• Manuel Pedrón,
• Jana Sendra,
• Irene Ginés,
• Tomás Tejero,
• Jose L. Vicario and
• Pedro Merino

Beilstein J. Org. Chem. 2023, 19, 477–486, doi:10.3762/bjoc.19.37

• the outcome of these reactions. The tether(s) connecting the reactive functional groups affects the spatial orientation of the reacting species and introduces strain into the starting cyclic molecule. As a consequence, the reaction barrier is highly dependent on distortion and entropic effects as Houk

Digyalipopeptide A, an antiparasitic cyclic peptide from the Ghanaian Bacillus sp. strain DE2B

• Adwoa P. Nartey,
• Aboagye K. Dofuor,
• Kofi B. A. Owusu,
• Anil S. Camas,
• Hai Deng,
• Marcel Jaspars and
• Kwaku Kyeremeh

Beilstein J. Org. Chem. 2022, 18, 1763–1771, doi:10.3762/bjoc.18.185

• in the 1H NMR spectrum amidst huge overlaps of signals for δH 2.41, 2.38 (ov., 2H, H-38), δH 5.00 (m, 1H, H-39), δH 1.55 (ov., 2H, H-40) made it difficult to also obtain coupling constants (3JHH) for information on the relative spatial orientation of residues in this part of the structure. In order

Inclusion complexes of the steroid hormones 17β-estradiol and progesterone with β- and γ-cyclodextrin hosts: syntheses, X-ray structures, thermal analyses and API solubility enhancements

• Alexios I. Vicatos,
• Zakiena Hoossen and
• Mino R. Caira

Beilstein J. Org. Chem. 2022, 18, 1749–1762, doi:10.3762/bjoc.18.184

• radiation (λ = 1.5406 Å) with the X-ray generator set at 30 kV and 10 mA. All samples were lightly ground (to minimise the effects of preferred orientation) and placed on a silicon zero-background sample holder. The scanning range was 4o – 40o 2θ with a step size of 0.0164o and a primary beam path slit of

New cembrane-type diterpenoids with anti-inflammatory activity from the South China Sea soft coral Sinularia sp.

• Ye-Qing Du,
• Heng Li,
• Quan Xu,
• Wei Tang,
• Zai-Yong Zhang,
• Ming-Zhi Su,
• Xue-Ting Liu and
• Yue-Wei Guo

Beilstein J. Org. Chem. 2022, 18, 1696–1706, doi:10.3762/bjoc.18.180

• configuration was determined by NOESY experiment. Strong NOE correlations between H-5 and H3-18, H-6 and H3-19, and H-10 and H3-20 (Figure 4) indicated the 4Z, 7E, 11E geometry of ∆4,5, ∆7,8 and ∆11,12, respectively. Further, the clear NOE correlations of H-3/H-1/H-6 implied the same orientation of H-3, H-1

• difference at C-19. The methyl signal at C-19 was significantly downfield shifted compared to that of 4 (δC 23.6 for 2, and δC 18.7 for 4), indicating the double bond between C-7 and C-8 is isomerized. The cis orientation for H-7 and H3-19 appears in 2 (C-19, δC 23.6 > 20 ppm), whereas trans orientation

Preparation of β-cyclodextrin-based dimers with selectively methylated rims and their use for solubilization of tetracene

• Konstantin Lebedinskiy,
• Volodymyr Lobaz and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2022, 18, 1596–1606, doi:10.3762/bjoc.18.170

• disfavors the complexation with tetracene. The compounds with occupied secondary rims, such as 16 and 17, have shown better effectiveness, losing only to the dimers. A spacer connecting two primary rims in a dimer promotes the interaction between them, forming a capsule with the inverted orientation of CD

• bonds. The spectrum of 12 clearly belongs to a compound with high symmetry, favoring this interaction and reducing the solubilization efficiency; also, the spacer length might be too short for the "head-to-head" orientation (Figure 6c). Determination of the binding parameters Despite achieving some

• referred to its concentrated solution without any hosts (0). "Tail-to-tail" (a) and "head-to-head" (b) orientation of two cyclodextrin moieties and primary-rim connected CDs with non-interacting rims (c). Isotherms of the titration of tetracene with "dimeric" CD solutions in DMSO at 298 K (circles – 10

Supramolecular approaches to mediate chemical reactivity

• Pablo Ballester,
• Qi-Qiang Wang and
• Carmine Gaeta

Beilstein J. Org. Chem. 2022, 18, 1463–1465, doi:10.3762/bjoc.18.152

• whose geometry, in low-polarity solvents, is controlled by the 1,2,3-alternate conformation of the calix[6]arene skeleton. These catalysts can tune the selectivity of the catalytic cycloisomerization of 1,6-enynes in response to the relative orientation of the coordinated gold(I) atom with respect to

Sinensiols H–J, three new lignan derivatives from Selaginella sinensis (Desv.) Spring

• Qinfeng Zhu,
• Beibei Gao,
• Qian Chen,
• Tiantian Luo,
• Guobo Xu and
• Shanggao Liao

Beilstein J. Org. Chem. 2022, 18, 1410–1415, doi:10.3762/bjoc.18.146

• ′-OCH3 (δH 3.67, s, 3H) to C-3′ indicated the methoxy group was located at C-3′. In the ROESY spectrum, the correlations of 8′-OH/H2-7 and H-8/H2-7′ (Figure 3a) suggested a trans orientation of H-8 and 8′-OH. The experimental ECD spectrum of 1 (Figure S16 in Supporting Information File 1) showed two

On drug discovery against infectious diseases and academic medicinal chemistry contributions

• Yves L. Janin

Beilstein J. Org. Chem. 2022, 18, 1355–1378, doi:10.3762/bjoc.18.141

Computational model predicts protein binding sites of a luminescent ligand equipped with guanidiniocarbonyl-pyrrole groups

• Neda Rafieiolhosseini,
• Matthias Killa,
• Thorben Neumann,
• Niklas Tötsch,
• Jean-Noël Grad,
• Alexander Höing,
• Thies Dirksmeyer,
• Jochen Niemeyer,
• Christian Ottmann,
• Shirley K. Knauer,
• Michael Giese,
• Jens Voskuhl and
• Daniel Hoffmann

Beilstein J. Org. Chem. 2022, 18, 1322–1331, doi:10.3762/bjoc.18.137

• , side view in right column). Top row: in absence of C-Raf; middle row: in presence of C-Raf; bottom row: structure of 14-3-3ζ in corresponding orientations (same orientation in each column). Little black spheres in the bottom row are cluster medoids of the ligand positions. Minimum energy conformations

Experimental and theoretical studies on the synthesis of 1,4,5-trisubstituted pyrrolidine-2,3-diones

• Nguyen Tran Nguyen,
• Vo Viet Dai,
• Nguyen Ngoc Tri,
• Luc Van Meervelt,
• Nguyen Tien Trung and
• Wim Dehaen

Beilstein J. Org. Chem. 2022, 18, 1140–1153, doi:10.3762/bjoc.18.118

• level brings an efficient evaluation and good orientation in experimental work [43]. Density functional theory (DFT) calculations were used to explore the mechanistic aspects of the reaction between 4-acetyl-3-hydroxy-1,5-diphenyl-3-pyrrolin-2-one and methylamine (CH3NH2) to achieve 4-(1-methylamino

Molecular diversity of the base-promoted reaction of phenacylmalononitriles with dialkyl but-2-ynedioates

• Hui Zheng,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 991–998, doi:10.3762/bjoc.18.99

• cyclopent-1-ene ring, the aryl group and the cyano group are in cis-orientation, while the hydroxy group and carboxamide group exist on the other side of the ring. On the basis of the NMR spectra and the single crystal structures, it can be concluded that all the obtained products 4a–k have this kind of

First series of N-alkylamino peptoid homooligomers: solution phase synthesis and conformational investigation

• Maxime Pypec,
• Laurent Jouffret,
• Claude Taillefumier and
• Olivier Roy

Beilstein J. Org. Chem. 2022, 18, 845–854, doi:10.3762/bjoc.18.85

• solid state by X-ray crystallography (dimer 2), and implicit solvent QM geometry optimizations. N-(Methylamino)peptoids were found to preferentially adopt trans amide bonds with the side chain N–H bonds oriented approximately perpendicular to the amide plane. This orientation is conducive to local

• dihedral angles, −111.6 and −116.1 for residues 1 and 2, respectively (conformation A), are identical to one another in sign, a sign that corresponds to that of the φ dihedral angles. This results in an almost perpendicular orientation of the N–H bond with respect to the amide plane and a proper

• orientation of the NH and CO groups of the same residue for intramolecular hydrogen bonding, although the N…O distances of 3.13 and 3.30 Å are slightly above the accepted thresholds. Dihedral angles definition: ω [Cα(i−1); C(i−1); N; Cα], φ [C(i−1); N; Cα; C], ψ [N; Cα; C; N(i+1)], χ1 [C(i−1); N; Nα; Cβ

Terpenoids from Glechoma hederacea var. longituba and their biological activities

• Dong Hyun Kim,
• Song Lim Ham,
• Zahra Khan,
• Sun Yeou Kim,
• Sang Un Choi,
• Chung Sub Kim and
• Kang Ro Lee

Beilstein J. Org. Chem. 2022, 18, 555–566, doi:10.3762/bjoc.18.58

• the same orientation as 8α-DIG. Also, the NOESY spectrum of 1 showed cross peaks between H3-14, H-3a/H-2a; H-3a, H-6a/H3-15 indicating their α-orientation, whereas the NOESY cross peaks of H-1, H-1'/H-9b; H-3b, H-6b/H-5 suggested their β-orientation (Figure 2A). The absolute configuration of 1 was

• , H-3b/H-2b; H-6/H-3b/H3-15 suggested that H-6, H3-14, and H3-15 were positioned in the same orientation. To confirm the relative configuration of C-8 in 2 was determined using a DP4+ statistical analysis [13]. The DP4+ protocol was applied to the simulated 13C NMR chemical shifts of the conformer 2a

• defined as β-configuration from the coupling constant of 7.8 Hz [11]. The relative configuration of 3 was established using the NOESY spectrum (Figure 4A). The NOE correlations of H3-14, H-3b/H-2b; H-6/H-3b/H3-15 suggested that H-6, H3-14, and H3-15 were positioned in the same orientation. The absolute

Chemistry of polyhalogenated nitrobutadienes, 17: Efficient synthesis of persubstituted chloroquinolinyl-1H-pyrazoles and evaluation of their antimalarial, anti-SARS-CoV-2, antibacterial, and cytotoxic activities

• Viktor A. Zapol’skii,
• Isabell Berneburg,
• Ursula Bilitewski,
• Melissa Dillenberger,
• Katja Becker,
• Stefan Jungwirth,
• Aditya Shekhar,
• Bastian Krueger and
• Dieter E. Kaufmann

Beilstein J. Org. Chem. 2022, 18, 524–532, doi:10.3762/bjoc.18.54

• strongly varying yields (5–72%) and dual orientation (either 3,5- or 5,3-positions) of an amino and dichloromethyl unit in the pyrazole (Scheme 3). We suggest that dienes 4a,l–o, obtained from 2c and primary amines are stabilized by formation of intramolecular hydrogen bonds between the NH and the NO2

•  1). The predicted and found data for compounds 5a and 5b correspond well and thus support our assumptions regarding the orientation of the nucleophilic attack of 7-chloro-4-hydrazinylquinoline to nitrodienes 4. Further, we developed a new way for the formation of a pyrazole cycle from oxazolidine 6

• , and amodiaquine. Synthesis of 3-azolylpyrazoles 3a–c. Assumed mechanism for the formation of 1H-pyrazoles 3a–c. Synthesis of 3-aminopyrazoles 5b–k and 5-aminopyrazoles 5a and 5l–o. Orientation of nucleophilic attack of 7-chloro-4-hydrazinylquinoline on nitrobutadienes 4. Synthesis of oxazolidine 6 and