N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• chlorinated product 21 was detected, which with POCl3 gave the cyclized product 22. Also, the synthesis of benzo[b]thieno[2,3-c]quinolone 24 as an anticancer molecule was demonstrated in this approach (Scheme 13). An intermolecular sulfenoamination of alkenes 9 with sulfonamides 25 as the nitrogen source and

• the presence of N-(2-bromophenylthio)succinimide 1’ and copper catalyst led to intermolecular sulfenoamination of alkenes and subsequent C–N coupling to produce dihydrobenzothiazine structures 27 in a one-pot manner. Furthermore, deprotection of the amine unit by K2CO3 and Na metal was performed in

• alcohols. Arylthiolation of arylamines with (arylthio)-pyrrolidine-2,5-diones. Catalyst-free isothiocyanatoalkylthiation of styrenes. Sulfenylation of (E)-β-chlorovinyl ketones toward 3,4-dimercaptofurans. HCl-promoted intermolecular 1, 2-thiofunctionalization of aromatic alkenes. Possible mechanism for

Cyclization of 1-aryl-4,4,4-trichlorobut-2-en-1-ones into 3-trichloromethylindan-1-ones in triflic acid

• Vladislav A. Sokolov,
• Andrei A. Golushko,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2023, 19, 1460–1470, doi:10.3762/bjoc.19.105

• interesting rearrangement with the intermolecular transfer of a phenyl group in the starting methoxy-substituted enone 2j under the rather harsh reaction conditions (TfOH at 80 °C). To study the cyclization further, reactions of some hydroxy ketones 1 were run for shorter time (1–4.5 h) in TfOH at 80 °C, i.e

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

• directly related with the overlap integral between HOMO and LUMO orbitals and influences the energy differences between first singlet and triplet excited states [14]. Therefore, we expect a marked difference in the photophysical properties for 4BGIPN, vide infra. Analysis of the intermolecular interactions

• revealed that 4BGIPN molecules experience face to face intermolecular π–π stacking interactions between the benzoguanidine moieties similar to 4CzIPN (reported by Etherington et al., [12]). The average interplanar distance for close neighbor benzoguanidine moieties in 4BGIPN is 3.322(3) Å, which is

• significantly shorter (0.4 Å) than the 3.74(3) Å average distance between nearest neighbor carbazole ligands in 4CzIPN, indicative for much stronger intermolecular interactions. Cyclic voltammetry was used to analyze the redox behavior of 4BGIPN in THF solution containing [n-Bu4N]PF6 as supporting electrolyte

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• , where the byproducts typically associated with free carbene formation (e.g., dimerization or rearrangement) were not observed (Scheme 2). In 1988, Hadjiarapoglou was investigating transition metal- and photocatalyzed intermolecular cyclopropanations between ylide 8 and norbornene, and found indane 9 was

• reductive elimination of iodobenzene to give 11 (Figure 5, left). This was also the pathway subsequently suggested by Gallos et al. [116] for the synthesis of 13/14 from 12. In 2003, Hadjiarapoglou further investigated the intermolecular reaction between 8 and cyclopentene under thermal, metal-free

• acceptor [61]. Beyond simply considering the strength of these bonds, other characteristics of this interaction should directly impact the outcomes of the reactions that they undergo. For instance, Mulliken’s initial description of an intermolecular halogen bond was of a charge transfer complex (also known

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

• ). Nucleophilic addition of the amine to the acyl radical and amine-assisted intermolecular proton transfer [84] generates the α-hydroxy radical 24 from which formation of the amide 25 proceeds either via i) oxidation by [Ir2]+ and deprotonation or ii) radical chain propagation [85]. Electron-deficient, electron

Aromatic C–H bond functionalization through organocatalyzed asymmetric intermolecular aza-Friedel–Crafts reaction: a recent update

• Anup Biswas

Beilstein J. Org. Chem. 2023, 19, 956–981, doi:10.3762/bjoc.19.72

• expansion of the substrate scope was demonstrated by incorporating a β-naphthol ring as the C3 substituent of the indole moiety (substrate 73). In all classes of bi(heteroaryl) substrates, a phenolic OH group at the ortho-position was crucial as it was involved in an intermolecular hydrogen bonding with the

• potential electrophiles, N-methoxycarbonyl-substituted aldimines 105 were explored to activate the para-carbon of the phenol derivatives catalyzed by the chiral pyrophosphoric acid Py1. The high regioselectivity was mainly caused by catalyst–substrate interactions via intermolecular H-bonding which could

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

• proximal C–H functionalizations in pyridine substrates under different catalytic systems. However, the intermolecular undirected distal C–H functionalization in pyridine remained unstudied. In these circumstances, the distal C–H alkylation by addition of the pyridine C–H bond to an aldehyde 50 under

• reactions are very scarcely reported which specifically include the intramolecular C–H alkylation of pyridine with alkenes at the C3 or C4 positions. Hence, very recently in 2022, Shi and co-workers [64] adopted an intermolecular process and reported the enantioselective para-alkylation of pyridines with

• styrenes 64 using a Ni–Al bimetallic system and NHC ligand 65 through intermolecular hydroarylation with high levels of enantio- and regioselectivity in the alkylated products 66 (Scheme 13). Also, the authors performed DFT studies revealing the reaction mechanism and supported that the interaction of the

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

• aldol addition step was performed either in a two-component (intramolecular aldol) or a three-component (intermolecular aldol) arrangement. The enantioselective implementation of this methodology was realized by Herraiz and Cramer in 2021 (Scheme 53) [98]. The reaction sequence is initiated by the C–H

• activation of aryl pyrazoles, followed by the asymmetric conjugate addition to the Michael acceptor. Then, the formed cobalt enolate participates in the intermolecular aldol reaction with an aldehyde 207. The stereochemistry of this tandem procedure is controlled by the chiral Co(III) complex C4 bearing

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

• ]. Excimers are formed when pyrene moieties form supramolecular complexes by intermolecular or intramolecular π–π interactions, causing a significant shift of single pyrene bands to longer wavelengths. Pyrenes are often used as a sensor part of receptor molecules, so their excimer bands switch on/off to

• applications [9]. These compounds have a very large aromatic surface suitable to form self-assembled supramolecular structures by intermolecular π–π interactions and showed excimer fluorescence in thin film and in the solid state. Kawai et al. reported exciplex formation between pyrene and guanine in polar

• decrease of UV–vis spectra upon heating up to 90 °C and a baseline increase indicated intermolecular stacking and aggregation of compounds, which was more pronounced for Phen-Py-2. Spectroscopic characterization data are given in the Table 1 and Supporting Information File 1, Figure S1. A linker between

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

• product 19c, the latter was obtained in a greatly reduced yield, perhaps due to less ring strain providing a thermodynamic driving force. In 2013, Mannathan et al. discussed a Ni-catalyzed intermolecular three-component difunctionalization of oxabicyclic alkenes 1 with organoboronic acids 20 and alkynes

• 25. Transmetalation of 25 with the organoboronic acid gives intermediate 26, which upon reductive elimination affords the difunctionalized product 21 and regenerates the Ni(0) catalyst. In 2019, the Stanley laboratory explored the Ni-catalyzed intermolecular three-component carboacylation of

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

• also carried out an analysis of the electron localization function (ELF) [31][32] and the charge transfer along the reaction coordinate to determine the different stages and the polarity of the reaction. Results and Discussion The enantioselective intermolecular cycloaddition between hydrazones and

• groups the global charge transfer is not so high to be considered a polar process. The reaction, as previously reported by the classical intermolecular reaction takes place smoothly by the action of the organocatalyst that renders a protonated hydrazone as the reacting functional group. However, in

CuAAC-inspired synthesis of 1,2,3-triazole-bridged porphyrin conjugates: an overview

• Dileep Kumar Singh

Beilstein J. Org. Chem. 2023, 19, 349–379, doi:10.3762/bjoc.19.29

• porphyrin groups were observed in nonpolar solvents. In addition, UV–vis and fluorescence spectra also showed that the 1,2,3-triazole moiety can stabilize zinc porphyrin by forming an intermolecular coordination complex. Also, it was found that porphyrin complex 160 is easy to synthesize, is fat soluble and

• . Furthermore, these two structurally similar porphyrins 166a,b were used as hosts for the intermolecular formation of inclusion complexes with tetrasodium tetraphenylporphyrintetrasulfonate 132 in aqueous solution, leading to the constructions of two different nanoarchitectures with alternating porphyrin and

An accelerated Rauhut–Currier dimerization enabled the synthesis of (±)-incarvilleatone and anticancer studies

• Tharun K. Kotammagari,
• Sweta Misra,
• Sayantan Paul,
• Sunita Kunte,
• Rajesh G. Gonnade,
• Manas K. Santra and
• Asish K. Bhattacharya

Beilstein J. Org. Chem. 2023, 19, 204–211, doi:10.3762/bjoc.19.19

• (±)-rengyolone (3). Despite of these syntheses, the synthesis of the dimeric natural product (±)-incarvilleatone (1), whose monomeric unit (±)-rengyolone (3) was connected by accelerated intermolecular Rauhut–Currier (RC) reaction was not reported in literature. Herein, we present the total synthesis of

• ) dimerization has some limitations, such as its controlling selectivity for intermolecular reactions in differently activated alkenes, and low reactivity. Han and co-workers [6] addressed the latter one by designing a substrate in which nucleophile functionality is also present in the Michael acceptor to

• accelerate the reaction. In conventional intermolecular RC reactions, the reaction proceeds by the intermolecular addition of a nucleophilic catalyst to the enone substrate to generate an enolate in the first step. In the second step the enolate ion attacks the other Michael acceptor at β-position in an

1,4-Dithianes: attractive C2-building blocks for the synthesis of complex molecular architectures

• Bram Ryckaert,
• Ellen Demeyere,
• Frederick Degroote,
• Hilde Janssens and
• Johan M. Winne

Beilstein J. Org. Chem. 2023, 19, 115–132, doi:10.3762/bjoc.19.12

• simple linear vinyl disulfone (Scheme 8a), and by intermolecular competition experiments it was shown to be about as reactive as maleic anhydride. Benzo-1,4-dithiin-1,1,4,4-tetraoxide (7) also serves as an excellent acetylene equivalent through desulfonylation with sodium amalgam. The non-benzo-fused

• intermolecular allyl cation-type cycloadditions (Scheme 14b–d) [103]. At first, this was investigated for its use in typical (4 + 3) cycloadditions with dienes, but mixed results were obtained (Scheme 14b). Whereas other heteroatom-stabilized allyl cations, such as oxathiins developed by Harmata, or furans

• use in intermolecular cycloadditions, as the putative gold(I)-coordinated intermediates like 112 are indeed quite similar to those expected to arise from dihydrodithiin alcohol 90 (see Scheme 19) [112]. However, our results with the simple 2-ethynyl-1,3-dithiolane (116) immediately showed that the

NaI/PPh₃-catalyzed visible-light-mediated decarboxylative radical cascade cyclization of N-arylacrylamides for the efficient synthesis of quaternary oxindoles

• Dan Liu,
• Yue Zhao and
• Frederic W. Patureau

Beilstein J. Org. Chem. 2023, 19, 57–65, doi:10.3762/bjoc.19.5

• run in a similar fashion to related well-documented previous reports [54][68][69][70][71][72][73][74][75][76][77], through a light-induced, phosphine-assisted, intermolecular electron transfer from sodium iodide to the redox-active ester. Conclusion In summary, we developed an effective photocatalytic

Synthetic study toward tridachiapyrone B

• Morgan Cormier,
• Florian Hernvann and
• Michaël De Paolis

Beilstein J. Org. Chem. 2022, 18, 1741–1748, doi:10.3762/bjoc.18.183

• investigation, it is mostly restricted to substrates bearing a tertiary alkoxy group [34]. Few examples of this intermolecular strategy actually involve substrates containing a quaternary carbon and the formation of a C–C bond [35][36]. Of note was the report of Takemoto and Iwata describing the 1,4-addition of

A novel bis-triazole scaffold accessed via two tandem [3 + 2] cycloaddition events including an uncatalyzed, room temperature azide–alkyne click reaction

• Ksenia Malkova,
• Andrey Bubyrev,
• Vasilisa Krivovicheva,
• Dmitry Dar’in,
• Alexander Bunev and
• Mikhail Krasavin

Beilstein J. Org. Chem. 2022, 18, 1636–1641, doi:10.3762/bjoc.18.175

• in Scheme 1 speaks for the unusual facility with which the intramolecular azide–alkyne click reaction took place. Normally, intermolecular click reactions are copper-catalyzed [17][18][19][20]. Intramolecular positioning of the click reaction partners may eliminate the need for the metal-based

Synthesis of (−)-halichonic acid and (−)-halichonic acid B

• Keith P. Reber and
• Emma L. Niner

Beilstein J. Org. Chem. 2022, 18, 1629–1635, doi:10.3762/bjoc.18.174

• elimination to form an alkene or intermolecular nucleophilic attack by formic acid (ultimately giving a formate ester) are reasonable mechanistically, only the intramolecular nucleophilic attack by the carbonyl group of the pendent ethyl ester was observed in this system to form the resonance-stabilized

Comparison of crystal structure and DFT calculations of triferrocenyl trithiophosphite’s conformance

• Ruslan P. Shekurov,
• Mikhail N. Khrizanforov,
• Ilya A. Bezkishko,
• Tatiana P. Gerasimova,
• Almaz A. Zagidullin,
• Daut R. Islamov and
• Vasili A. Miluykov

Beilstein J. Org. Chem. 2022, 18, 1499–1504, doi:10.3762/bjoc.18.157

• a negative charge at the Fe ion and positive charges at hydrogen atoms (Figure 3). Thus the crystal structure of (FcS)3P is defined rather by plural intermolecular interactions than by relative energetics of conformers (Figures S1–S3 in Supporting Information File 1). Previously, for triferrocenyl

• C–H···O interactions, respectively, are observed. It should be noted that (FcS)3PO crystals contain a solvent molecule that participates in intermolecular interactions. Thus, despite the similarity of the molecular structure of the three compounds and some crystal parameters, the intermolecular

• has the highest energy. Most obviously the latter is stabilized by intermolecular C–H···π interactions (Figures S4 and S5 in Supporting Information File 1). The bulky Fc moieties do not allow to form such type of dimers. Conclusion Triferrocenyl trithiophosphite (FcS)3P was studied by X-ray single

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

• characteristic of supramolecular catalysis is that the general modes of activation based on intermolecular interactions can operate on substrates in a selective way, and in confined environment, like the active site of natural enzymes [5][6][7][8][9][10][11][12][13][14]. As a result, molecular recognition of the

• of the capsules by means of intermolecular interactions. The most intriguing aspect of catalysis in confined spaces [5][6][7][8][9][10][11][12][13][14] is that the reactions can take place through unusual mechanisms. This is mainly due to the conformational control of the substrates, steric

• distributions when performed inside the containers compared to the bulk solution. As mentioned above, activation of substrates, stabilization of intermediates and transition states through intermolecular interactions was established as one of the fundamental factors of supramolecular catalysis, and among these

Oxa-Michael-initiated cascade reactions of levoglucosenone

• Julian Klepp,
• Thomas Bousfield,
• Hugh Cummins,
• Sarah V. A.-M. Legendre,
• Jason E. Camp and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2022, 18, 1457–1462, doi:10.3762/bjoc.18.151

• processes in 1, such as the Baylis–Hillman reaction [14], and the Rauhut–Currier reaction which gives dimers such as 2 as well as higher oligomers [10][15]. An oxa-Michael-initiated three-component intermolecular reaction of 1 with furfural and water has been reported to result in enone 3 (Figure 1) [16

• elimination of methanol rather than exocyclic elimination of water, and regioisomeric Rauhut–Currier reaction. Compound 7 was found to be unstable after isolation, possibly due to intermolecular reactions of the electron-poor olefin and furan ring. When a slight excess of 1 was used, only 6n was isolated

Dissecting Mechanochemistry III

• Lars Borchardt and
• José G. Hernández

Beilstein J. Org. Chem. 2022, 18, 1454–1456, doi:10.3762/bjoc.18.150

• intermolecular C–N coupling reactions using DDQ as an oxidant.

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

• diffuse intermolecular C–H···O contacts involving the phosphate and acetyl oxygen atoms. Deprotection of 16 was completed in two steps, first using hydrogenolysis with Adam’s catalyst (PtO2), followed by removal of the acetate protecting groups with Et3N/H2O/MeOH, and furnished the target glycosyl 1

Thermally activated delayed fluorescence (TADF) emitters: sensing and boosting spin-flipping by aggregation

• Ashish Kumar Mazumdar,
• Gyana Prakash Nanda,
• Nisha Yadav,
• Upasana Deori,
• Upasha Acharyya,
• Bahadur Sk and
• Pachaiyappan Rajamalli

Beilstein J. Org. Chem. 2022, 18, 1177–1187, doi:10.3762/bjoc.18.122

• solution and in the solid state and with multicolor tunability by external stimuli are crucial for task-specific applications. Recently, donor–acceptor (D–A)-based organic emitters have shown tunable optical and electrochemical properties due to alteration of the intermolecular charge-transfer (ICT

Synthesis, optical and electrochemical properties of (D–π)₂-type and (D–π)₂Ph-type fluorescent dyes

• Kosuke Takemura,
• Kazuki Ohira,
• Taiki Higashino,
• Keiichi Imato and
• Yousuke Ooyama

Beilstein J. Org. Chem. 2022, 18, 1047–1054, doi:10.3762/bjoc.18.106

• intermolecular π–π interactions between the fluorophores leading to delocalization of excitons or excimers in the solid state would be responsible for the bathochromic shifts of λmax,abs and λmax,fl and lowering of Φfl with change of state from solution to solid [34][35][36]. The τfl-solid values of OTK-2 and