Recent advances in total synthesis of illisimonin A

• Juan Huang and
• Ming Yang

Beilstein J. Org. Chem. 2025, 21, 2571–2583, doi:10.3762/bjoc.21.199

• of 85 with iodine and BnOH enabled the intermolecular iodoetherification to yield ketal 86. A KF-promoted intramolecular alkylation of the cyclopentadiene moiety then delivered compound 87. To introduce the C4 hydroxy group and C1 functional handle for further elaboration, a nitroso-Diels–Alder

Transformation of the cyclohexane ring to the cyclopentane fragment of biologically active compounds

• Natalya Akhmetdinova,
• Ilgiz Biktagirov and
• Liliya Kh. Faizullina

Beilstein J. Org. Chem. 2025, 21, 2416–2446, doi:10.3762/bjoc.21.185

• (benzil, semipinacol, with the participation of thallium- and iodine-based oxidants, photochemical, Wolff, Meinwald, Wagner–Meerwein and Favorskii) are presented. The review summarizes literature data covering the last 12 years, with some exceptions of earlier works due to the importance of the published

• and Favorskii reaction), using oxidants based on thallium and iodine, with a focus on recent works published in the period from 2014 to 2024. Review 1 Recyclization A common method for converting cyclohexene 1 into cyclopentene 2 is the ozonolytic cleavage of the double bond followed by intramolecular

• (III) and iodine(III), and Wolff rearrangement. 2.1 Benzilic acid and semipinacol-type rearrangements The strategy of ring contraction using the benzilic acid-type rearrangement was used by Zhang et al. [38] for the asymmetric synthesis of 4β-acetoxyprobotryane-9β,15α-diol (52). This compound contains

Conformational effects on iodide binding: a comparative study of flexible and rigid carbazole macrocyclic analogs

• Guang-Wei Zhang,
• Yong Zhang,
• Le Shi,
• Chuang Gao,
• Hong-Yu Li and
• Lei Xue

Beilstein J. Org. Chem. 2025, 21, 2369–2375, doi:10.3762/bjoc.21.181

• towards downfield, with a displacement of 0.6015 ppm to 8.5940 ppm. This phenomenon may be due to the formation of noncovalent bonds between the iodine ions encapsulated inside the macrocyclic and the hydrogen atoms on the macrocyclic framework, which reduces the density of the electron cloud of aromatic

• a/b and c/d both moved slightly to higher field. This indicates that there is a slight difference in the interaction between NH protons and iodine ions of the two structural analogs. Structural analysis showed that since the two single bonds are rotationally restricted, all its accessible

• when interacting with iodine ions, and that flexible PBGs enhance the host–guest complementarity through conformational adjustments, resulting in local conformational fitting changes [25]. To determine the binding ratios and binding constants of the two structural analogs to iodine ions, we designed a

Pathway economy in cyclization of 1,n-enynes

• Hezhen Han,
• Wenjie Mao,
• Bin Lin,
• Maosheng Cheng,
• Lu Yang and
• Yongxiang Liu

Beilstein J. Org. Chem. 2025, 21, 2260–2282, doi:10.3762/bjoc.21.173

• radical initiated intramolecular cascade cyclization of 1,n-enynes to provide structurally diverse heterocycles (Scheme 4) [11]. Solvent selection dictated divergent reaction pathways under I2/TBHP oxidation. When an acetonitrile/water mixed solvent was used, iodine radical addition to the alkyne

C2 to C6 biobased carbonyl platforms for fine chemistry

• Jingjing Jiang,
• Muhammad Noman Haider Tariq,
• Florence Popowycz,
• Yanlong Gu and
• Yves Queneau

Beilstein J. Org. Chem. 2025, 21, 2103–2172, doi:10.3762/bjoc.21.165

The application of desymmetric enantioselective reduction of cyclic 1,3-dicarbonyl compounds in the total synthesis of terpenoid and alkaloid natural products

• Dong-Xing Tan and
• Fu-She Han

Beilstein J. Org. Chem. 2025, 21, 2085–2102, doi:10.3762/bjoc.21.164

• reduction of 72, affording the hydroxyketone 74 in 57% yield with 91% ee. Protection of the secondary alcohol in 74 followed by Beckmann rearrangement led to lactam 75. Oxidation state modifications and functional group transformations of 75 afforded ketone 76. Next, the 1,2-addition of 76 with vinyl iodine

Bioinspired total syntheses of natural products: a personal adventure

• Zhengyi Qin,
• Yuting Yang,
• Nuran Yan,
• Xinyu Liang,
• Zhiyu Zhang,
• Yaxuan Duan,
• Huilin Li and
• Xuegong She

Beilstein J. Org. Chem. 2025, 21, 2048–2061, doi:10.3762/bjoc.21.160

• as a single isomer, which further underwent a migratory rearrangement and afforded iboluteine. On the other hand, oxidation of ibogaine with molecular iodine achieved both indole and amine oxidations, delivering lactam 35. Intermediate 35 could be oxidized with H2O2 through C–C bond cleavage to give

• proposed key transformations (Scheme 6). Starting from the diaryl-THF-type precursor 36 with a phenol moiety, oxidation of the phenol with hypervalent iodine reagent PIDA generated the putative oxa-carbenium intermediate 37, which successfully underwent the Friedel–Crafts cyclization to provide

Aryl iodane-induced cascade arylation–1,2-silyl shift–heterocyclization of propargylsilanes under copper catalysis

• Rasma Kroņkalne,
• Rūdolfs Beļaunieks,
• Armands Sebris,
• Anatoly Mishnev and
• Māris Turks

Beilstein J. Org. Chem. 2025, 21, 1984–1994, doi:10.3762/bjoc.21.154

• synthetic potential of iodane-mediated carbofunctionalization under copper catalysis. Keywords: arylation reactions; copper-catalysis; iodanes; propargylsilanes; 1,2-silyl shift; Introduction Highly electrophilic hypervalent iodine(III) reagents are considered as arene electrophilic synthons, making them

Photoswitches beyond azobenzene: a beginner’s guide

• Michela Marcon,
• Christoph Haag and
• Burkhard König

Beilstein J. Org. Chem. 2025, 21, 1808–1853, doi:10.3762/bjoc.21.143

• (37) followed by reduction with Zn/Ba(OH)2 and partial re-oxidation (Scheme 12A) [52]. They can also be obtained from o-halogenated benzyl bromides 40 by lithium–halogen exchange followed by nucleophilic substitution and a second lithium–halogen exchange with iodine (Scheme 12B) or by nickel-catalysed

Convenient alternative synthesis of the Malassezia-derived virulence factor malassezione and related compounds

• Karu Ramesh and
• Stephen L. Bearne

Beilstein J. Org. Chem. 2025, 21, 1730–1736, doi:10.3762/bjoc.21.135

• , ON, Canada). Reactions were monitored using thin-layer chromatography on aluminium-backed silica plates (Sigma-Aldrich) using either UV-light (254 nm), iodine, KMnO4, phosphomolybdic acid, or p-anisaldehyde for visualization. Tetrahydrofuran (THF) was dried and distilled over sodium/benzophenone

Reactions of acryl thioamides with iminoiodinanes as a one-step synthesis of N-sulfonyl-2,3-dihydro-1,2-thiazoles

• Vladimir G. Ilkin,
• Pavel S. Silaichev,
• Valeriy O. Filimonov,
• Tetyana V. Beryozkina,
• Margarita D. Likhacheva,
• Pavel A. Slepukhin,
• Wim Dehaen and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2025, 21, 1397–1403, doi:10.3762/bjoc.21.104

• ]. 2,5-Dihydro-1,2-thiazoles were synthesized by oxidative cyclization of N-arylamides of 3-(alkylamino)prop-2-enethiocarboxylic acids with iodine (Scheme 1А) [16]. 2,3-Dihydro-1,2-thiazoles were first synthesized in 1997 by the reaction of 2,2-dimethyl-N-alkylsulfonyl-N-benzylaminoacetonitrile with

Oxetanes: formation, reactivity and total syntheses of natural products

• Peter Gabko,
• Martin Kalník and
• Maroš Bella

Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101

• that it likely proceeds through a p-quinone methide intermediate 213. The authors also demonstrated on two selected examples (214) that the products could be further derivatised to 3-substituted benzofurans 215 and benzindoles 216 with a hypervalent iodine reagent. In 2022, Bull et al. disclosed a

Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents

• Jiangfei Chen,
• Yi-Lin Qu,
• Ming Yuan,
• Xiang-Mei Wu,
• Heng-Pei Jiang,
• Ying Fu and
• Shengrong Guo

Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98

• difluoroethylsulfinate (DFES-Na) to generate difluoroethyl radicals via anodic single-electron oxidation (Scheme 23) [14]. The method was evaluated with various N-arylacrylamides, revealing that substrates with different substituents, including fluorine, chlorine, bromine, and iodine, participated well in the reaction

Synthetic approach to borrelidin fragments: focus on key intermediates

• Yudhi Dwi Kurniawan,
• Zetryana Puteri Tachrim,
• Teni Ernawati,
• Faris Hermawan,
• Ima Nurasiyah and
• Muhammad Alfin Sulmantara

Beilstein J. Org. Chem. 2025, 21, 1135–1160, doi:10.3762/bjoc.21.91

• alcohols, 34 and ent-34, after recrystallization from hot hexane (100% ee by chiral phase HPLC, yield not reported). These alcohols were then treated with triphenylphosphine and iodine in the presence of imidazole to yield the iodides 35 and ent-35 (Scheme 2). The iodide intermediates were subsequently

Investigations of amination reactions on an antimalarial 1,2,4-triazolo[4,3-a]pyrazine scaffold

• Henry S. T. Smith,
• Ben Giuliani,
• Kanchana Wijesekera,
• Kah Yean Lum,
• Sandra Duffy,
• Aaron Lock,
• Jonathan M. White,
• Vicky M. Avery and
• Rohan A. Davis

Beilstein J. Org. Chem. 2025, 21, 1126–1134, doi:10.3762/bjoc.21.90

• et al. for 5-position halogenated scaffolds [10]. Several different triazolopyrazine compounds bearing chlorine, bromine or iodine at the 5-position, gave no ipso-substituted (5-substituted) products when refluxed in toluene with phenethylamine, with all major products being substituted at the 8

Supramolecular assembly of hypervalent iodine macrocycles and alkali metals

• Krishna Pandey,
• Lucas X. Orton,
• Grayson Venus,
• Waseem A. Hussain,
• Toby Woods,
• Lichang Wang and
• Kyle N. Plunkett

Beilstein J. Org. Chem. 2025, 21, 1095–1103, doi:10.3762/bjoc.21.87

• at Urbana-Champaign, Urbana, IL, 61801, United States 10.3762/bjoc.21.87 Abstract This study explores the solution- and solid-state assembly of phenylalanine-based hypervalent iodine macrocycles (HIMs) with lithium and sodium cations. The metal cation binding of HIMs was evaluated by addition of

• are presented. Keywords: hypervalent iodine; macrocycle; metal coordination; supramolecular; Introduction Supramolecular chemistry is emerging as a pivotal area of research in both medicinal and materials chemistry that opens the avenue for new functionalized materials for their use in medical

• chemistries of hypervalent iodine systems that involve secondary bonding to form higher order molecular assemblies are yet to be fully explored. In general, the atom’s capacity to extend its valence shell beyond the usual limitations of a Lewis octet is known as hypervalency [9]. The modern periodic table

Recent advances in synthetic approaches for bioactive cinnamic acid derivatives

• Betty A. Kustiana,
• Galuh Widiyarti and
• Teni Ernawati

Beilstein J. Org. Chem. 2025, 21, 1031–1086, doi:10.3762/bjoc.21.85

• active acid fluorides 48 by utilizing hypervalent iodine(III) of PhI(OPiv)2 and py·HF as the fluoride source to afford the corresponding amides 49 and 50 in excellent yields (Scheme 16) [48]. Herein, the hypervalent iodine(III) reagent reacted with the phenol group to give intermediates 51 and 52

• )-cinnamic acid esters 445–448 in excellent yields via E-to-Z photoisomerization mediated by the photocatalyst (Scheme 90) [152]. Nguyen and co-workers (2019) employed iodine to catalyze the intermolecular olefin-carbonyl metathesis reaction of benzaldehyde (449) and acrylate 450 to give the corresponding

On the photoluminescence in triarylmethyl-centered mono-, di-, and multiradicals

• Daniel Straub,
• Markus Gross,
• Mona E. Arnold,
• Julia Zolg and
• Alexander J. C. Kuehne

Beilstein J. Org. Chem. 2025, 21, 964–998, doi:10.3762/bjoc.21.80

• the time that they remain in their enantiopure state. The glum as a measure for the strength of CPL is of order 8 × 10−4 for PTM and 5 × 10−4 for TTM. Mixed halide triarylmethyl radicals Substitution of all para-positions in PTM with iodine atoms yields the 3I-PTM radical with a red-shifted emission

• by the heavy atom effect of iodine, that also allows intersystem crossing (ISC) between triplet states in the matrix and the emissive doublet states of 3I-PTM. Interestingly, functionalization of all three para-positions in TTM with chalcogens in the form of aryloxy- and aryl thioethers leads to

• iodine should break the symmetry; however, no effect on the absorption spectra and especially on the lower energy |D1⟩ transition has been reported [45]. Interestingly, substitution of one of the para-chlorines in TTM by iodine (I-TTM) has been reported to enable Pd-catalyzed cross-coupling, allowing

Chitosan-supported CuI-catalyzed cascade reaction of 2-halobenzoic acids and amidines for the synthesis of quinazolinones

• Xuhong Zhao,
• Weishuang Li,
• Mengli Yang,
• Bojie Li,
• Yaoyao Zhang,
• Lizhen Huang and
• Lei Zhu

Beilstein J. Org. Chem. 2025, 21, 839–844, doi:10.3762/bjoc.21.67

• 10.3762/bjoc.21.67 Abstract A chitosan-supported CuI (CS@CuI) catalyst was developed for the synthesis of quinazolinones from 2-halobenzoic acids (including iodine and bromine) and amidines. The reaction proceeds under mild reaction conditions, demonstrating a broad substrate scope (30 examples) and good

• methods, the cascade reaction between ortho-halogen (e.g., chlorine, bromine or iodine) substituted benzoic acids and amidines has become a prominent route to synthesize the corresponding quinazolinones [10][11][12][13][14][15][16][17][18]. In 2009, Fu and co-workers found that copper(I) could effectively

• analysis of the filtered aqueous solution after the reaction confirmed no detectable leaching of CuI. Conclusion In summary, we have developed a CS@CuI-catalyzed cascade reaction of 2-halobenzoic acids (including iodine and bromine derivatives) and amidines for the synthesis of quinazolinones. This

Recent advances in the electrochemical synthesis of organophosphorus compounds

• Babak Kaboudin,
• Milad Behroozi,
• Sepideh Sadighi and
• Fatemeh Asgharzadeh

Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61

• lower yield than the –Me group. This decrease in yield is likely due to the lower oxidation voltage of the –OMe group, which may lead to the formation of unwanted byproducts. The reaction began with an anodic oxidation of iodide to iodine, followed by a reaction with dialkyl phosphonate to give I–P(O

• -withdrawing groups such as –Cl, –Br, and –CO2Me. It was observed that carbazole derivatives with an extended conjugated system showed enhanced reactivity. Like the above P–N coupling mechanism, the reaction proceeded by an anodic oxidation of iodide to iodine followed by a reaction with dialkylphosphine oxide

• alkyl chain, both P(OiPr)3 and P(On-Bu)3 proved effective in this reaction. In this reaction, the P–N coupling process proceeded via forming an N-indole iodide intermediate via anodic oxidation of iodide to iodine, followed by a reaction with indole (Scheme 23). Cyclic voltammetry demonstrated that in

Synthesis of HBC fluorophores with an electrophilic handle for covalent attachment to Pepper RNA

• Raphael Bereiter and
• Ronald Micura

Beilstein J. Org. Chem. 2025, 21, 727–735, doi:10.3762/bjoc.21.56

• and iodine, respectively, were applied to compound 5 to give the chloropropyl and iodopropyl HBC dyes 12 and 13 (Scheme 4). In addition, the HBC alcohol 5 was reacted under basic conditions with methanesulfonyl chloride to give the N-(3-mesyloxypropyl) HBC derivative 14, or with tosyl chloride to give

Formaldehyde surrogates in multicomponent reactions

• Cecilia I. Attorresi,
• Javier A. Ramírez and
• Bernhard Westermann

Beilstein J. Org. Chem. 2025, 21, 564–595, doi:10.3762/bjoc.21.45

• was carried out via copper catalysis or iodine–acid catalysis. Interestingly, when aliphatic amines are employed (R3 = n-Pr, n-Bu, product 8) only the N atoms are incorporated in the structure of the final product, probably because the high temperature favors the elimination of the alkyl group. The

• DMSO (Scheme 12) [45]. In this case, the reaction works well under metal-free conditions using iodine as the catalyst. Remarkably, the activation of DMSO was accomplished using Selectfluor, and in this case, DMSO is the source of a C-1 unit. It is important to note that the reaction could be performed

Asymmetric synthesis of β-amino cyanoesters with contiguous tetrasubstituted carbon centers by halogen-bonding catalysis with chiral halonium salt

• Yasushi Yoshida,
• Maho Aono,
• Takashi Mino and
• Masami Sakamoto

Beilstein J. Org. Chem. 2025, 21, 547–555, doi:10.3762/bjoc.21.43

• -workers developed chiral amine 1 with an electron-deficient iodine atom, which catalyzed the Mannich reaction in excellent yields and enantioselectivities [17]. In 2020, Huber and co-workers reported the bis(iodoimidazolium) 2-catalyzed Mukaiyama–aldol reaction of carbonyl compounds with enol silyl ethers

Synthesis of electrophile-tethered preQ₁ analogs for covalent attachment to preQ₁ RNA

• Laurin Flemmich and
• Ronald Micura

Beilstein J. Org. Chem. 2025, 21, 483–489, doi:10.3762/bjoc.21.35

• subjected to Appel conditions in DMF, using elemental iodine as the halogen source. Notably, we were not able to efficiently generate the corresponding bromides with the same strategy. The preQ1 derivative 3a was synthesized in a 2-step reaction sequence analogous to the DPQ1 derivative 4b, while four steps

Electrochemical synthesis of cyclic biaryl λ³-bromanes from 2,2’-dibromobiphenyls

• Andrejs Savkins and
• Igors Sokolovs

Beilstein J. Org. Chem. 2025, 21, 451–457, doi:10.3762/bjoc.21.32

• approach would conceptually differ from previously reported anodic syntheses of cyclic diaryl iodonium compounds, where an electrochemically generated acyclic iodine(III) intermediate undergoes an intramolecular SEAr-type reaction to form the cyclic product [19][20]. Herein, we report on the development of