Giese-type alkylation of dehydroalanine derivatives via silane-mediated alkyl bromide activation

• Perry van der Heide,
• Michele Retini,
• Fabiola Fanini,
• Giovanni Piersanti,
• Francesco Secci,
• Daniele Mazzarella,
• Timothy Noël and
• Alberto Luridiana

Beilstein J. Org. Chem. 2024, 20, 3274–3280, doi:10.3762/bjoc.20.271

• slight increase in chemical yield. Giese reaction: Radical addition on olefins with an electron-withdrawing group (EWG) followed by a HAT or SET and protonation; halogen-atom transfer: (a) tin-mediated XAT, (b) XAT initiated by a photocatalyst (PC) and mediated by boranes (B), silanes (Si) or alkylamines

Efficient synthesis of fluorinated triphenylenes with enhanced arene–perfluoroarene interactions in columnar mesophases

• Yang Chen,
• Jiao He,
• Hang Lin,
• Hai-Feng Wang,
• Ping Hu,
• Bi-Qin Wang,
• Ke-Qing Zhao and
• Bertrand Donnio

Beilstein J. Org. Chem. 2024, 20, 3263–3273, doi:10.3762/bjoc.20.270

• is the same for all triphenylene derivatives. Thus, compound F crystallizes in an orthorhombic crystallographic system (Pccn space group, no. 56) [50] with unit cell dimensions a = 13.2645(2) Å, b = 5.5284(1) Å, and c = 22.7571(3) Å; the unit cell contains 8 molecules, which gives a calculated

• rather flat, with, however, a substantial planar deviation of the pending perfluorophenyl group, forming a large tilt of ca. 45°. From the view along the b-axis, it can be seen that the flat triphenylene cores stack perfectly on top of each other, but with the pending fluoroarene group being alternately

• Supporting Information File 1 (Figure S36). Comparative bar graph summarizing the thermal behavior of Fn, BTP6, and PHn derivatives (2nd heating DSC data). Representative S/WAXS patterns of Fn and Gnm compounds. Absorption (a) and emission (b) spectra of F6 and G66, measured in different solvents at a

Intramolecular C–H arylation of pyridine derivatives with a palladium catalyst for the synthesis of multiply fused heteroaromatic compounds

• Yuki Nakanishi,
• Shoichi Sugita,
• Kentaro Okano and
• Atsunori Mori

Beilstein J. Org. Chem. 2024, 20, 3256–3262, doi:10.3762/bjoc.20.269

• . Experimental Typical experimental procedure for the C–H arylation of pyridine derivative 5-octyldibenzo[b,f][1,7]naphthyridin-6(5H)-one (2a): To a screw-capped test tube equipped with a magnetic stirring bar were added amide 1a (44.1 mg, 0.100 mmol), potassium carbonate (42.0 mg, 0.304 mmol

Non-covalent organocatalyzed enantioselective cyclization reactions of α,β-unsaturated imines

• Sergio Torres-Oya and
• Mercedes Zurro

Beilstein J. Org. Chem. 2024, 20, 3221–3255, doi:10.3762/bjoc.20.268

• hydrogen bonding with the protonated tertiary amine. Then, a Michael addition of malononitrile to the azadiene takes place to obtain exclusively the (S)-intermediate A. Subsequently an intramolecular nucleophilic addition of the nitrile leads to the intermediate B, which undergoes tautomerization to

• the bifunctional squaramide enables a stereoselective Michael addition of the azlactone to the azadiene forming intermediate A which transforms into intermediate B, which then undergoes an intramolecular cyclization to give the desired product 20. In 2020, Ni, Song and co-workers described a

• the nitrogen atoms. Then, the azlactone enolate undergoes a nucleophilic attack on its Si-face via Mannich reaction with the 2-benzothiazolimine leading to intermediate A which evolves toward its resonance form B, responsible of the intramolecular attack of the negatively charged nitrogen to the

Ceratinadin G, a new psammaplysin derivative possessing a cyano group from a sponge of the genus Pseudoceratina

• Shin-ichiro Kurimoto,
• Kouta Inoue,
• Taito Ohno and
• Takaaki Kubota

Beilstein J. Org. Chem. 2024, 20, 3215–3220, doi:10.3762/bjoc.20.267

• (partial structures a and b, respectively, in Figure 2), which were characteristic of psammaplysins, in ceratinadin G (1) was suggested by comparison of its 1H and 13C NMR data with those of known psammaplysin derivatives such as psammaplysins A and F (2) [4][5][6][10][11][12]. HMBC correlations (H-1/C-2

• b in Figure 2) was confirmed by the 1H-1H COSY and TOCSY correlations (C-10–C-12 and C-19–C-20), and HMBC correlations (H2-12/C-13, H-15/C-14 (H-17/C-18), H-15/C-19 (H-17/C-19), H-17/C-13 (H-15/C-13), H-17/C-15 (H-15/C-17), and H2-20/C-16). HMBC correlations between the N-methyl protons H3-21 (δH

Discovery of ianthelliformisamines D–G from the sponge Suberea ianthelliformis and the total synthesis of ianthelliformisamine D

• Sasha Hayes,
• Yaoying Lu,
• Bernd H. A. Rehm and
• Rohan A. Davis

Beilstein J. Org. Chem. 2024, 20, 3205–3214, doi:10.3762/bjoc.20.266

• , followed by isocratic conditions of 100% MeOH (0.1% TFA) for a further 10 min, all at a flowrate of 9 mL/min; 60 fractions (60 × 1 min) were collected. This first HPLC fractionation afforded ianthelliformisamine B (2, 10.4 mg, tR 36–37 min, 0.104% dry wt) and several other UV-active fractions that

Germanyl triazoles as a platform for CuAAC diversification and chemoselective orthogonal cross-coupling

• John M. Halford-McGuff,
• Thomas M. Richardson,
• Aidan P. McKay,
• Frederik Peschke,
• Glenn A. Burley and
• Allan J. B. Watson

Beilstein J. Org. Chem. 2024, 20, 3198–3204, doi:10.3762/bjoc.20.265

• John M. Halford-McGuff Thomas M. Richardson Aidan P. McKay Frederik Peschke Glenn A. Burley Allan J. B. Watson EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK Department of Pure & Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK

• (1.0 equiv), azide (1.1 equiv), CuSO4·5H2O (5.0 mol %), NaAsc (50 mol %), NEt3 (1.0 equiv), t-BuOH/H2O 1:1 (250 mM), N2, rt, 16 h. Isolated yields. aReaction performed with CsF (2.0 equiv) as an additive. bReaction performed at rt for 64 h. (a) Application of Ge-alkyne CuAAC to functional molecules. (b

• equiv), DMF, air, rt, 2 h. (iv) Pd(dtbpf)Cl2 (10 mol %), 2-acetylthiophen-3-ylboronic acid (1.2 equiv), K3PO4 (2.0 equiv), iPrOH/H2O 3:4, N2, 85 °C, 16 h. (v) Pd(dtbpf)Cl2 (2.0 mol %), 1-naphthylzinc bromide (1.2 equiv), THF, N2, 45 °C, 16 h. (vi) Cu(OAc)2·H2O (30 mol %), B(OH)3 (2.0 equiv), DBU (2.0

Synthesis of 2H-azirine-2,2-dicarboxylic acids and their derivatives

• Anastasiya V. Agafonova,
• Mikhail S. Novikov and
• Alexander F. Khlebnikov

Beilstein J. Org. Chem. 2024, 20, 3191–3197, doi:10.3762/bjoc.20.264

• single-crystal X-ray diffraction analysis. The reaction of azetidine with diacyl chloride 2a gave a complex mixture of products, and O-methyl hydroxylamine did not react. Diacyl chloride 2a reacts with methanol and ethanol to give diesters 11a,b (Scheme 5). An experiment with isoxazole 1a and methanol on

Direct trifluoroethylation of carbonyl sulfoxonium ylides using hypervalent iodine compounds

• Radell Echemendía,
• Carlee A. Montgomery,
• Fabio Cuzzucoli,
• Antonio C. B. Burtoloso and
• Graham K. Murphy

Beilstein J. Org. Chem. 2024, 20, 3182–3190, doi:10.3762/bjoc.20.263

• Radell Echemendia Carlee A. Montgomery Fabio Cuzzucoli Antonio C. B. Burtoloso Graham K. Murphy São Carlos Institute of Chemistry, University of São Paulo, 13560-970, São Carlos, SP, Brazil Department of Chemistry, University of Waterloo, 200 University Ave W., Waterloo, Ontario, Canada

• reductive elimination (path 1) [37][38][39]. This pathway initiates by formation of a halogen bond complex between 1a and the trifuoroethyl(mesityl)iodonium ion 2a’, where adduct XB-1 is presumably in equilibrium with isomeric XB-2. Reductive elimination of the iodoarene from XB-2 would furnish B, whose

• deprotonation would complete the pathway. The alternative mechanistic proposal is an SN2 reaction [40][41][42] between 1a and the iodonium ion 2a’, which directly furnishes B without invoking halogen bonded adducts. To assess which of these mechanistic possibilities was more probable, we turned to computational

Multicomponent reactions driving the discovery and optimization of agents targeting central nervous system pathologies

• Lucía Campos-Prieto,
• Aitor García-Rey,
• Eddy Sotelo and
• Ana Mallo-Abreu

Beilstein J. Org. Chem. 2024, 20, 3151–3173, doi:10.3762/bjoc.20.261

• various tissues, with a prominent expression in the adult brain, where it contributes to metabolic processes, aging, and epigenetic regulation. In this context, the group of Hasaninejad et al. (2017) [49] described the synthesis of spirooxindole, spiroacenaphthylene, and bisbenzo[b]pyran derivatives using

• of the nitrogen in lactams 11 with an oxygen in 12 to influence hydrogen-bond donating properties and synthesis of the benzodioxepinone derivatives via Passerini reaction. MCR 3 + 2 reaction to develop spirooxindole, spiroacenaphthylene, and bisbenzo[b]pyran compounds. Synthesis of ML192 analogs

Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF₅- and CF₃SF₄-containing [2]staffanes

• Jón Atiba Buldt,
• Wang-Yeuk Kong,
• Yannick Kraemer,
• Masiel M. Belsuzarri,
• Ansh Hiten Patel,
• James C. Fettinger,
• Dean J. Tantillo and
• Cody Ross Pitts

Beilstein J. Org. Chem. 2024, 20, 3134–3143, doi:10.3762/bjoc.20.259

• initial measurement of 3 at 90 K revealed an unusually large unit cell (a = 7.14 Å, b = 21.38 Å, and c = 44.04 Å). Following structure solution and refinement [76], we found that 3 crystallizes in an orthorhombic space group P212121 with five symmetry independent moieties (Z' = 5) and with no solvent

• , we confirmed that a phase transition had occurred following structure determination at 240 K [78][79]. The X-ray data revealed that 3 crystallizes in the centrosymmetric orthorhombic space group Pnma in the high temperature phase (HTP) with cell axes a = 21.56 Å, b = 8.95 Å, and c = 7.28 Å, in

• contrast to P212121 in the low temperature phase (LTP). Note that the b-axis is roughly 1/5 of the c-axis observed at 90 K (the axial rearrangement is due to the change in space group). To discern the approximate temperature of the phase transition, the unit cell was measured in 20 K increments upon

Hypervalent iodine-mediated intramolecular alkene halocyclisation

• Charu Bansal,
• Oliver Ruggles,
• Albert C. Rowett and
• Alastair J. J. Lennox

Beilstein J. Org. Chem. 2024, 20, 3113–3133, doi:10.3762/bjoc.20.258

• cost effective and selective, one-pot transformation. Pharmaceutical uses for bio-active cyclic molecules accessible by I(III) reagents are plentiful; anticancer drugs can be formed from the basis of pyrrolo[2,3-b]indoles 1 [3][4], 2-oxazolines 2 [5][6], dihydrofuran 3 [7][8], and spirocyclic scaffolds

• fluoride ion to displace PhI. In pathway B (bottom), the nitrogen is oxidised by the iodane, generating an electrophilic intermediate B. Nucleophilic attack by the double bond subsequently forms the 6-membered ring intermediate C, which is either immediately attacked by fluoride to form both cis and trans

• proposed by the authors (Scheme 3). Activation of the HVI reagent by H-bonding leads to ligand exchange to give an aminofluoro iodonium intermediate A. Cyclisation occurs via nitrogen attack on the alkene to then give aziridinium intermediate B. Subsequent nucleophilic attack by fluoride on the more

Advances in the use of metal-free tetrapyrrolic macrocycles as catalysts

• Mandeep K. Chahal

Beilstein J. Org. Chem. 2024, 20, 3085–3112, doi:10.3762/bjoc.20.257

• and a photosensitizer, facilitating photoinduced electron transfer (PET) to form the active cation radical B, and intersystem crossing (ISC) for energy transfer to generate the triplet carbene C. Radical B then reacted with biradical C, producing the new radical D, which accepted an electron from the

• porphyrin radical anion. Ultimately, protonation of intermediate E led to the final product. Formation of intermediates, such as enamine A and cation radical B, was confirmed using techniques like ESIMS, 1H NMR, and EPR, Stern–Volmer quenching experiments, respectively. All these mechanistic studies

• binding of O2 to diprotonated forms of porphyrins, 1092+ (H4FAP2+) and 182+ (H4TPP2+), which are then reduced in the organic phase by ferrocene-based reductants, resulting in H2O2, Fc+/DMFc+, and the respective metal-free porphyrin macrocycle (Figure 20a and b). The conditions of homogeneous O2 reduction

Enantioselective regiospecific addition of propargyltrichlorosilane to aldehydes catalyzed by biisoquinoline N,N’-dioxide

• Noble Brako,
• Sreerag Moorkkannur Narayanan,
• Amber Burns,
• Layla Auter,
• Valentino Cesiliano,
• Rajeev Prabhakar and
• Norito Takenaka

Beilstein J. Org. Chem. 2024, 20, 3069–3076, doi:10.3762/bjoc.20.255

• propargyltrichlorosilane without N,N-diisopropylethylamine and (b) with N,N-diisopropylethylamine. It includes Gibbs free energies (kcal/mol) and Mulliken charges (in parentheses). Metallotropic rearrangement and regioselectivity issues. Asymmetric catalytic allenylation of aldehydes. Selective preparation of

Extension of the π-system of monoaryl-substituted norbornadienes with acetylene bridges: influence on the photochemical conversion and storage of light energy

• Robin Schulte,
• Dustin Schade,
• Thomas Paululat,
• Till J. B. Zähringer,
• Christoph Kerzig and
• Heiko Ihmels

Beilstein J. Org. Chem. 2024, 20, 3061–3068, doi:10.3762/bjoc.20.254

• Robin Schulte Dustin Schade Thomas Paululat Till J. B. Zahringer Christoph Kerzig Heiko Ihmels Department of Chemistry-Biology, Center of Micro- and Nanochemistry and (Bio-)Technology (Cµ), University of Siegen, Adolf-Reichwein-Str. 2, 57068 Siegen, Germany Department of Chemistry, Johannes

• derivatives during the photoreaction, whereas the blue-shifted maximum of the photoproduct was formed. In addition, isosbestic points were observed for the derivatives 1h (A), 1i (B), 1k (D), and 1l (E). The irradiations of the derivatives 1h, 1i, 1k, and 1l were stopped once no more changes of the absorbance

• bis- and tris-norbornadienyl-substituted benzene derivatives. Photometric monitoring of the irradiation of 1h (A), 1i (B), 1j (C), 1k (D), 1l (E), and 1n (F); λex = 315 nm (1h, 1i, 1k, and 1l) or 340 nm (1j, 1n). Insets: plot of absorption at long-wavelength maximum versus irradiation time t

Chemical structure metagenomics of microbial natural products: surveying nonribosomal peptides and beyond

• Thomas Ma and
• John Chu

Beilstein J. Org. Chem. 2024, 20, 3050–3060, doi:10.3762/bjoc.20.253

• ) Incorporation of the first five amino acid BBs in daptomycin (highlighted in blue) is illustrated herein. In NRP biosynthesis, modules are arranged in an assembly line fashion; each module incorporates one BB into the growing peptide intermediate, which is then passed onto the next module. b) Within each module

• NRP is released from the enzymatic assembly line via a thioesterase (TE)-catalyzed nucleophilic attack. Depending on the nature of the nucleophile, this reaction may generate distinct NRP topologies and the five most common types are shown above. b) Cartoon illustration of the five most common NRP

Cyclodextrin-based rotaxanes for polymer materials: challenge on simultaneous realization of inexpensive production and defined structures

• Yosuke Akae

Beilstein J. Org. Chem. 2024, 20, 3026–3049, doi:10.3762/bjoc.20.252

• proceeds through the formation of CD and an axle molecule, followed by the end-capping of the axle end; (2) the slipping method (route b) involving threading a dumbbell molecule comprising bulky axle-end groups through CD. As the latter is likely to produce a pseudorotaxane framework, the end-capping

• the urea end-capping synthesis method (Figure 9) [46][47]. First, [3]rotaxane 3 synthesized using 2-bromophenyl isocyanate (yield: 73%) was confirmed to be a size-complementary rotaxane whose desilippage was observed in a DMSO solvent by heating at approximately 80 °C (Figure 9A,B). As the

• effect was caused by the non-covered axle-end groups by the conventional CDs on the [3]rotaxane framework, whereas the plus effect was induced by the partially covered axle-end groups by the acylated CDs (Figure 11A,B). On the former, two CD units interact on the center of the alkyl chain via hydrogen

Tunable full-color dual-state (solution and solid) emission of push–pull molecules containing the 1-pyrindane moiety

• Anastasia I. Ershova,
• Sergey V. Fedoseev,
• Konstantin V. Lipin,
• Mikhail Yu. Ievlev,
• Oleg E. Nasakin and
• Oleg V. Ershov

Beilstein J. Org. Chem. 2024, 20, 3016–3025, doi:10.3762/bjoc.20.251

• pyrindane – (E)-7-arylmethylene-2-chloro-6,7-dihydro-5H-cyclopenta[b]pyridine-3,4-dicarbonitriles – was developed. Tunable full-color emission was achieved for the synthesized push–pull molecules, solely by changing donor groups while keeping both the conjugated system and acceptor part of the molecule

• the facile preparation of molecular libraries with an emphasis on skeletal diversity for the development of new push–pull molecules. Results and Discussion Synthesis and structure determination A two-step procedure was used to obtain the target compounds (Scheme 1). Cyclopenta[b]pyridine derivative 2

Tailored charge-neutral self-assembled L₂Zn₂ container for taming oxalate

• David Ocklenburg and
• David Van Craen

Beilstein J. Org. Chem. 2024, 20, 3007–3015, doi:10.3762/bjoc.20.250

• reaction). b) Performed backbone modification to tackle this issue and to tame oxalate as the most competitive dicarboxylate guest with a charge-neutral metallocontainer. Recognition of mono- and dicarboxylates with [L2Zn2] which results in the formation of 1:1 host–guest complexes in case of clean binding

• which is observed for acetate, benzoate, and oxalate. a) 1H NMR titration (500 MHz, 500 µM, DMSO-d6, 25 °C) of [L2Zn2] with oxalate showing intermediate-like exchange. b) Negative ESI-MS spectrum of [L2Zn2] with 5 equiv oxalate showing the formation of [(C2)@L2Zn2]2− as host–guest complex. a) Optimized

• structure (ωB97X‒D4 [83]/def2-SVP [84][85], implicit solvation with DMSO [86], ORCA 5.0.3 [81][82]) of [(C2)@L2Zn2]2− showing a “meso-helicate” structure with oxalate coordinating to both zinc centers in a chelating fashion. b) 2D NOE contacts between Htriazole and Hquinolate (Hg···Ha). 1H NMR competition

Advances in radical peroxidation with hydroperoxides

• Oleg V. Bityukov,
• Pavel Yu. Serdyuchenko,
• Andrey S. Kirillov,
• Gennady I. Nikishin,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249

• then reacts with tert-butylperoxy radical B to form the target peroxide 20 and Cu(I). Cu(I) is oxidized by TBHP to form Cu(II) and tert-butoxy radical C, which abstracts a hydrogen atom from TBHP to form tert-butylperoxy radical B. Radical B can also be formed via oxidation of TBHP by complex A or the

• ) species react with TBHP, resulting in the formation of a peroxocomplex of TBHP with Co(III) (stage B). The oxidation of 4-hydroxy-2(5H)-furanone 21 by Co(III)OO-t-Bu complex generates the target product 22 (step C). A second reaction pathway is also possible, in which the tert-butoxy radical A abstracts

• presented in Scheme 12. The reaction probably begins with the oxidation of M(II) by TBHP into M(III) to form the tert-butoxy radical A, which abstracts a hydrogen atom from the substrate, generating the C-centered radical B. Peroxocomplex C, which can be formed from M(III)OH and TBHP as a result of ligand

Synthesis of fluorinated acid-functionalized, electron-rich nickel porphyrins

• Mike Brockmann,
• Jonas Lobbel,
• Lara Unterriker and
• Rainer Herges

Beilstein J. Org. Chem. 2024, 20, 2954–2958, doi:10.3762/bjoc.20.248

• ether synthesis with 2-hydroxy-3,4,5-trimethoxybenzaldehyde (21). Conditions: a) K2CO3, benzyl bromide, abs. MeCN, N2, reflux, 18 h; b) TEMPO, KBr, NaOCl, NaHCO3, MeCN, rt, 76 h; c) MeOH, H2SO4, reflux, 18 h; d) Pd/C, H2, EtOH, rt, 24 h; e) Tf2O, pyridine, DCM, rt, 18 h. Synthesis of perfluoroalkyl

• ester-functionalized aldehydes 22, 23, and 24. Conditions: a) NIS, TFA, Na2CO3, MeCN, reflux, 18 h; b) Cu2O·H2O, 2-pyridinaldoxime, TBAB, CsOH, H2O, N2, rt, 18 h; c) Cs2CO3, DMAc, N2, rt, 3 h. Porphyrin synthesis. a) Rothemund porphyrin synthesis of metal-free porphyrins 26, 27, and 28; b) metalation of

• porphyrins with Ni(acac)2; c) ester hydrolysis to generate the free acids 32, 33, and 34. Conditions: a) 1) 22/23/24, TFA, abs. DCM, N2, reflux, 30 min, 2) pyrrole, reflux, 2.5 h, 3) DDQ, reflux, 2 h; b) Ni(acac)2, toluene, reflux, 20 h; c) 1) LiOH, MeOH, rt, 1 h, 2) HCl. Supporting Information Supporting

Structure and thermal stability of phosphorus-iodonium ylids

• Andrew Greener,
• Stephen P. Argent,
• Coby J. Clarke and
• Miriam L. O’Duill

Beilstein J. Org. Chem. 2024, 20, 2931–2939, doi:10.3762/bjoc.20.245

• by the absence of a trans effect. While studies by Ochiai and Suresh found that strong sigma donors X cause a lengthening and weakening of the trans I–R bond in R–I(Ar)–X iodanes [32][33], little variation is observed in the I–C(ylid) (b) and I–C(arene) (c) bonds across the range of compounds

• )triphenylphosphonium salt 6 and (iodomethyl)triphenyl-phosphonium salt 7. Homolytic or heterolytic scission of the I–C(ylid) bond with loss of ArI (path a) would result in a carbene, though it is unclear how this would transform to compound 6. Alternatively, scission of the I–C(Ar) bond with loss of benzyne (path b

• -iodonium ylids at 10 °C min−1 in N2 (full dataset in Supporting Information File 1). (b) First derivatives of TGA thermograms normalised to the intensity of the first peak. (c) Correlation of Tonset with the dihedral angle φ (between the R–I–X bond and the plane of the arene substituent). (d–g) DSC

The charge transport properties of dicyanomethylene-functionalised violanthrone derivatives

• Sondos A. J. Almahmoud,
• Joseph Cameron,
• Dylan Wilkinson,
• Michele Cariello,
• Claire Wilson,
• Alan A. Wiles,
• Peter J. Skabara and
• Graeme Cooke

Beilstein J. Org. Chem. 2024, 20, 2921–2930, doi:10.3762/bjoc.20.244

• 16,17-dihydroxyviolanthrone with 2-ethylhexyl bromide (a), 1-bromooctane (b), and 1-bromododecane (c) resulting in compounds, 2a, 2b and 2c, respectively. The final target compounds 3a–c were synthesised in 13%, 48% and 36% yield, respectively, following the reported procedure for anthraquinone, where

• theoretical studies [32] (Table S1 in Supporting Information File 1). Molecules of 3b form stacks along the b-axis linked by π–π interactions with centroid–centroid distances of 3.65 and 3.98 Å. These stacks lie in sheets with alternating aromatic–aliphatic layers (Figure S3 in Supporting Information File 1

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• base-mediated deprotonation of substrates 86 produces the corresponding ester enolate. This enolate undergoes a retro-Michael reaction, generating sulfenate anion A. The sulfenate anion A then nucleophilically attacks the diaryliodonium salts 16, forming hypervalent iodine intermediates B. Finally

• temperature for 18 h, the yield was quite high (conditions A) [92]. Meanwhile, a similar yield was obtained in 2 h, when NaOH (conditions B) was used as a base (R2 = acyl). Upon moving to other substrates (R2 = aryl), the yield dropped significantly. By replacing the strong base with K2CO3, (conditions C) the

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

• purification process must be carried out under the mentioned personal protective equipment. The reaction on a larger scale is carried out under special safety conditions [57][58][59]. 3-(Cyclohexylamino)-2-phenyldibenzo[b,f]pyrrolo[1,2-d][1,4]oxazepine-1-carbonitrile (4a); ethyl 2-(4-chlorophenyl)-3

• -(cyclohexylamino)dibenzo[b,f]pyrrolo[1,2-d][1,4]thiazepine-1-carboxylate (4l) and 11-(cyclohexylamino)-12-phenyl-9H-benzo[f]pyrrolo[1,2-d][1,2,3]triazolo[1,5-a][1,4]diazepine-13-carbonitrile (6a); typical procedure: Cyclic imines of dibenzo[b,f][1,4]oxazepine 3a–c, dibenzo[b,f][1,4]thiazepine 3d, and 4H-benzo[f

• nuclear magnetic resonance) spectra of compound 6f (DMSO-d6, 300 MHz) at 25–85 °C; spectrum A: 25 °C, spectrum B: 35 °C, spectrum C: 45 °C, spectrum D: 55 °C, spectrum E: 65 °C, spectrum F: 75 °C and spectrum E: 85 °C. The crystal structure of 6a (CCDC2365306). UV–vis absorption for compounds 4a, 6c and