Synthesis of pyrrole-fused dibenzoxazepine/dibenzothiazepine/triazolobenzodiazepine derivatives via isocyanide-based multicomponent reactions

• Marzieh Norouzi,
• Mohammad Taghi Nazeri,
• Ahmad Shaabani and
• Behrouz Notash

Beilstein J. Org. Chem. 2024, 20, 2870–2882, doi:10.3762/bjoc.20.241

• ) [42][43]. Another I-MCR for forming pyrroles is the in situ formation reaction of the zwitterion III, known as Huisgens 1,4-dipole. The latter is formed by the reaction of imines with acetylenedicarboxylates and can be trapped by an isocyanide through a [4 + 1] cyclization reaction to synthesize

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

• limitation, we analyzed the mechanism underlying the formation of resorcin[n]arenes. The first step of the cyclization reaction is a hydroxyalkylation involving various cationic intermediates [69]. Hence, we hypothesized that any factor enhancing the rate of the first step by stabilizing carbocations will

• -substitued resorcinols are notoriously difficult to engage in the cyclization reaction towards resorcin[n]arenes since the nucleophilic character of the attacking aromatic carbon is diminished. Specifically, there is no literature information on 2-chlororesorcinol or 2-iodoresorcinol being used in this

Photoredox-catalyzed intramolecular nucleophilic amidation of alkenes with β-lactams

• Valentina Giraldi,
• Giandomenico Magagnano,
• Daria Giacomini,
• Pier Giorgio Cozzi and
• Andrea Gualandi

Beilstein J. Org. Chem. 2024, 20, 2461–2468, doi:10.3762/bjoc.20.210

• variants. A) Access of clavam derivatives by intramolecular photoredox reaction of alkenes. B) Clavulanic acid and its derivatives. C) Construction of the oxacepham scaffold by radical cyclization. Tentative mechanism for the photo-cyclization reaction. Preparation of alkenyl β-lactam derivatives for the

Hypervalent iodine-mediated cyclization of bishomoallylamides to prolinols

• Smaher E. Butt,
• Konrad Kepski,
• Jean-Marc Sotiropoulos and
• Wesley J. Moran

Beilstein J. Org. Chem. 2024, 20, 2455–2460, doi:10.3762/bjoc.20.209

• . Optimized structures are shown for the cyclization transition states (hydrogen atoms are omitted for clarity and bond lengths are given in Å). Scope of cyclization reaction. Reactions of di- and trisubstituted alkene substrates. Optimization of cyclization reaction. Supporting Information Supporting

Evaluating the halogen bonding strength of a iodoloisoxazolium(III) salt

• Dominik L. Reinhard,
• Anna Schmidt,
• Marc Sons,
• Julian Wolf,
• Elric Engelage and
• Stefan M. Huber

Beilstein J. Org. Chem. 2024, 20, 2401–2407, doi:10.3762/bjoc.20.204

• )AuCl was applied with a catalyst loading of 2 mol %, activated by an equal amount of the DAI salt. Due to solubility issues, the reaction had to be performed in methylene chloride instead of chloroform. The gold-catalyzed cyclization reaction (Scheme 2) was followed via 1H NMR spectroscopy (Figure 3

Efficacy of radical reactions of isocyanides with heteroatom radicals in organic synthesis

• Akiya Ogawa and
• Yuki Yamamoto

Beilstein J. Org. Chem. 2024, 20, 2114–2128, doi:10.3762/bjoc.20.182

• radical, which induces 5-exo cyclization. The following hydrogen abstraction, intramolecular ionic cyclization, and hydrolysis during chromatography on silica gel affords the cyclic amide in good yield. They further applied this radical cyclization reaction as a key step in the synthesis of (±)-α-kainic

• isocyanates In the case of o-alkenyl isocyanides, it has already been described that the 5-exo cyclization reaction proceeds selectively, yielding nitrogen-containing 5-membered cyclic products. In sharp contrast, when the photoirradiated reaction of ortho-alkynyl isocyanides was carried out, we found that an

• in which phosphorus-centered radicals generated from diarylphosphine oxides by Mn(OAc)3-assisted oxidation [94] or the photoredox system [95][96][97] were used in the radical cyclization reaction of 2-isocyanobiaryls (Scheme 24). Yadav and Sigh et al. reported the direct synthesis of 6-sulfonylated

Electrochemical radical cation aza-Wacker cyclizations

• Sota Adachi and
• Yohei Okada

Beilstein J. Org. Chem. 2024, 20, 1900–1905, doi:10.3762/bjoc.20.165

• chromatography (hexane/ethyl acetate) gave the corresponding ring compounds. Cyclic voltammograms for aryl sulfonamides. Radical and ionic intramolecular cyclizations. Electrochemical and photochemical aza-Wacker cyclizations. Scope of electrochemical aza-Wacker cyclization. Reaction conditions: the alkene (0.20

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

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

• -toluenesulfonic acid-mediated hydrolysis led to the cyclization reaction yielding the steroidal 17-spiro derivatives. The procedure was applied to synthesize drospirenone (Figure 1) and extended to build the spirolactone 23 from DHEA, a key intermediate toward the popular diuretic spironolactone (Scheme 7). 17

• process, the carbonyl group at C-17 was stereoselectively attacked by α-lithio-α-methoxyallene at −78 °C to produce allene 25. A further cyclization reaction was induced by potassium tert-butoxide in the presence of catalytic dicyclohexyl-18-crown-6. The final 17-spirodihydro-(2H)-furan-3-one 27 was

Phenotellurazine redox catalysts: elements of design for radical cross-dehydrogenative coupling reactions

• Alina Paffen,
• Christopher Cremer and
• Frederic W. Patureau

Beilstein J. Org. Chem. 2024, 20, 1292–1297, doi:10.3762/bjoc.20.112

• reaction [6][7], and Gabbaï yet another in a different cyclization reaction [8][9], among other catalytic chalcogen bonding activation examples [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29]. In contrast, we have reported recently some redox-active Te-based catalysts

• enabling the activation of small yet highly relevant organic substrates. For example, Huber and co-authors recently designed a Te-based catalyst in an indole Michael addition reaction [1][2][3][4][5]. Pale and Mamane utilized another Te-based catalyst in an electrophilic bromine-mediated cyclization

Mechanistic investigations of polyaza[7]helicene in photoredox and energy transfer catalysis

• Johannes Rocker,
• Till J. B. Zähringer,
• Matthias Schmitz,
• Till Opatz and
• Christoph Kerzig

Beilstein J. Org. Chem. 2024, 20, 1236–1245, doi:10.3762/bjoc.20.106

• Information File 1). A remarkable turnover number of 4440 was achieved when 1 M stilbene was used (see Supporting Information File 1 for more information). Furthermore, the photocatalyst was utilized in a photosensitized cyclization reaction of cinnamyl chloride [84]. This photoreaction was originally

Carbonylative synthesis and functionalization of indoles

• Alex De Salvo,
• Raffaella Mancuso and
• Xiao-Feng Wu

Beilstein J. Org. Chem. 2024, 20, 973–1000, doi:10.3762/bjoc.20.87

• of amides from 2-alkynylanilines by using TFBen (benzene-1,3,5-triyl triformate) as a CO source, Pd(OAc)2, DPEPhos (bis[(2-diphenylphosphino)phenyl] ether), and DIPEA (N,N-diisopropylethylamine) in MeCN. After 24 h, Pd(OAc)2 and AlCl3 were added to promote a selective cyclization reaction [14]. The

• reductive elimination and the generated Pd(0) species gets oxidated by the oxygen to the active Pd(II) species (Scheme 7). Synthesis of indoles by metal-catalyzed reductive cyclization reaction of organic nitro compounds with carbon monoxide as reductant In the last 60 years, the metal-catalyzed

•  28). Metal-catalyzed carbonylative cyclization reaction of indole derivatives In 2016, Guo and co-workers, in the same work in which different examples of 6H-isoindolo[2,1-a]indol-6-ones were reported, performed the synthesis of indeno[1,2-b]indol-10(5H)-ones from 2-(2-bromophenyl)-1-alkyl-1H-indoles

Palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines

• Geng-Xin Liu,
• Xiao-Ting Jie,
• Ge-Jun Niu,
• Li-Sheng Yang,
• Xing-Lin Li,
• Jian Luo and
• Wen-Hao Hu

Beilstein J. Org. Chem. 2024, 20, 661–671, doi:10.3762/bjoc.20.59

• % yield. Compound 4a could be hydrogenated to the corresponding reduction product 12 using Pd/C and ammonium formate conditions (Scheme 6a). Notably, as shown in Scheme 6b, treatment of the unsaturated γ-AA derivative 6a with Pd/C and ammonium formate led to a cyclization reaction, furnishing γ-lactam 13

Photoinduced in situ generation of DNA-targeting ligands: DNA-binding and DNA-photodamaging properties of benzo[c]quinolizinium ions

• Julika Schlosser,
• Olga Fedorova,
• Yuri Fedorov and
• Heiko Ihmels

Beilstein J. Org. Chem. 2024, 20, 101–117, doi:10.3762/bjoc.20.11

• photoinduced cyclization reaction of readily available styrylpyridine derivatives 2a–g gives the corresponding benzo[c]quinolizinium derivatives and that these reactions are more efficient in aqueous solutions than in organic solvents. The benzo[c]quinolizinium derivatives have the typical properties of DNA

Recent advancements in iodide/phosphine-mediated photoredox radical reactions

• Tinglan Liu,
• Yu Zhou,
• Junhong Tang and
• Chengming Wang

Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131

• ], it was proposed that the decarboxylative cascade cyclization reaction proceeded through the formation of a charge-transfer complex (CTC) II involving PPh3, NaI, and NHP ester 3 (Scheme 20). Upon photofragmentation of the CTC complex II, two important intermediates were generated: an alkyl radical A

Synthesis and biological evaluation of Argemone mexicana-inspired antimicrobials

• Jessica Villegas,
• Bryce C. Ball,
• Katelyn M. Shouse,
• Caleb W. VanArragon,
• Ashley N. Wasserman,
• Hannah E. Bhakta,
• Allen G. Oliver,
• Danielle A. Orozco-Nunnelly and
• Jeffrey M. Pruet

Beilstein J. Org. Chem. 2023, 19, 1511–1524, doi:10.3762/bjoc.19.108

• the amount of CuSO4, as well as the timing of its addition to the cyclization reaction, hoping to limit the oxidation side reaction. This was indeed beneficial, as the B3/B4 ratio changed from 50:50 to >95% formation of B3. Interestingly, all attempts at rerunning the reaction that produced B2 under

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

• in the cyclization reaction. The role of these prenyl side chains has been partially investigated, but remains elusive in the cyclization cascade. In this study, we focus on variexenol B that is synthesized from iso-GGPP, as recently reported by Dickschat and co-workers, and investigate the

• 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

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

• construction of 4-chalcogenylated pyrazoles 57 and 59 was carried out starting from α,β-alkynic hydrazones 55 (Scheme 24) [60]. In the procedure, α,β-alkynic hydrazones were subjected to S- or Se-electrophiles 56 and cyclization reaction. Additionally, NCS and ArSH produced the S-electrophile for the

• cyclization reaction with arylpropynal hydrazones. Also, the reaction of 1-(1,3-diphenylprop-2-yn-1-ylidene)-2-phenylhydrazine 58 as the substrate with N-sulfenylsuccinimides 1 afforded fully substituted pyrazoles 59 in up to 98% yield. In 2021, a solvent-controllable approach for the construction of 3

Selective construction of dispiro[indoline-3,2'-quinoline-3',3''-indoline] and dispiro[indoline-3,2'-pyrrole-3',3''-indoline] via three-component reaction

• Ziying Xiao,
• Fengshun Xu,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 1234–1242, doi:10.3762/bjoc.19.91

• showed that the carbonyl group of the dimedone does not take part in the further cyclization reaction, while the carbonyl group of the benzoyl group participated in the annulation reaction to give the pyrrolidyl ring. This result clearly indicated that the adducts of 3-phenacylideneoxindoles showed

Photoredox catalysis enabling decarboxylative radical cyclization of γ,γ-dimethylallyltryptophan (DMAT) derivatives: formal synthesis of 6,7-secoagroclavine

• Alessio Regni,
• Francesca Bartoccini and
• Giovanni Piersanti

Beilstein J. Org. Chem. 2023, 19, 918–927, doi:10.3762/bjoc.19.70

• intramolecularly with the C4-pendant prenyl side-chain previously oxidized [76]. Closure of the photoredox catalytic cycle would then involve SET reduction, and protonation would deliver the desired carbocyclic ring (Figure 1c). If this cyclization reaction could be realized in either way, it would shorten the

First synthesis of acylated nitrocyclopropanes

• Kento Iwai,
• Rikiya Kamidate,
• Khimiya Wada,
• Haruyasu Asahara and
• Nagatoshi Nishiwaki

Beilstein J. Org. Chem. 2023, 19, 892–900, doi:10.3762/bjoc.19.67

• cyclization reaction using 4e by 1H NMR. Versatile reactivities of cyclopropanes 1a. Preparative methods for cyclopropanedicarboxylates 1a. Bromination of ethyl acetoacetate (3c) and reaction with nitrostyrene 2a. Reaction of 4b with (diacetoxyiodo)benzene (top); structural determination of product 9 (bottom

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

• . systematically modified atropisomeric C1-symmetric stack ligands to identify suitable catalytic systems for a highly enantioselective synthesis of organoboranes (Scheme 42) [83]. Their best attempt to realize a tandem borylation/aldol cyclization reaction resulted in 72% yield, 90% ee, and a diastereomeric ratio

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

• scaffolds 147 through a domino ARO reaction followed by cyclization reaction of oxabicyclic alkenes 30 with sodium cyanate (146) (Scheme 26) [72]. This reaction proceeded smoothly with electron-rich oxabenzonorbornadiene derivatives; however, electron-poor oxabenzonorbornadiene derivatives resulted in

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

• formation occurs during the other reacting basin’s evolution. During the process, N12 loses its lone pair which is involved in the C5–N12 bond formation, and after the cyclization reaction, in a second stage, the lone pair is recovered after the proton (H13) is abstracted by the phosphoric acid. As expected

Catalytic aza-Nazarov cyclization reactions to access α-methylene-γ-lactam heterocycles

• Bilge Banu Yagci,
• Selin Ezgi Donmez,
• Onur Şahin and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2023, 19, 66–77, doi:10.3762/bjoc.19.6

• or more heteroatoms in the dienone core have the potential to provide efficient access to a variety of heterocyclic scaffolds. Among such variants, the aza-Nazarov reaction appears as a highly suitable cyclization reaction that presents opportunities for the construction of a diverse array of five