A convergent synthetic approach to the tetracyclic core framework of khayanolide-type limonoids

• Zhiyang Zhang,
• Jialei Hu,
• Hanfeng Ding,
• Li Zhang and
• Peirong Rao

Beilstein J. Org. Chem. 2025, 21, 926–934, doi:10.3762/bjoc.21.75

• achieved by using (R)-BTM (19), furnishing acetate 18 with satisfactory efficiency and enantioselectivity (37% yield, 85% ee). Finally, iodination of 18 employing Johnsen’s protocol (I2, pyridine) [39] provided α-iodoenone 13 in 89% yield. On the other hand, the synthesis of acetal aldehyde 14 commenced with

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

• reaction proceeded with electrophilic iodination of aromatic compounds followed by a nucleophilic reaction of the formed phosphorothioate intermediate to give corresponding S-heteroaryl phosphorothioates in good to excellent yields (Scheme 29). In 2023, Liu et al. [70] reported an interesting

• , followed by the iodination reaction of aromatic compounds (Scheme 31). In the next step, elemental selenium was inserted into the aryl iodide bond to form the aryl iodoselenide intermediate for forming the P–Se bond. Other electrochemical reactions of organophosphorus Li et al. [72] reported an

Asymmetric synthesis of fluorinated derivatives of aromatic and γ-branched amino acids via a chiral Ni(II) complex

• Maurizio Iannuzzi,
• Thomas Hohmann,
• Michael Dyrks,
• Kilian Haoues,
• Katarzyna Salamon-Krokosz and
• Beate Koksch

Beilstein J. Org. Chem. 2025, 21, 659–669, doi:10.3762/bjoc.21.52

• synthesis of alkyl iodides was investigated. A tosylate functionality was employed as a leaving group in the iodination reaction. Finally, the desired fluorinated tosylate 9 could be isolated on a gram-scale in a moderate yield of 27% (Scheme 3a). Subsequently, the iodination of the tosylate has been

Total synthesis of (±)-simonsol C using dearomatization as key reaction under acidic conditions

• Xiao-Yang Bi,
• Xiao-Shuai Yang,
• Shan-Shan Chen,
• Jia-Jun Sui,
• Zhao-Nan Cai,
• Yong-Ming Chuan and
• Hong-Bo Qin

Beilstein J. Org. Chem. 2025, 21, 601–606, doi:10.3762/bjoc.21.47

• , successfully forming the aryl-containing quaternary center. However, in this step, the reaction was too rapid to control. After optimizing the reaction time and temperature, the reaction was carried out at −30 °C for 15 minutes and product 14 was isolated in a yield as high as 58% [14]. Iodination of compound

Synthesis of acenaphthylene-fused heteroarenes and polyoxygenated benzo[j]fluoranthenes via a Pd-catalyzed Suzuki–Miyaura/C–H arylation cascade

• Merve Yence,
• Dilgam Ahmadli,
• Damla Surmeli,
• Umut Mert Karacaoğlu,
• Sujit Pal and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2024, 20, 3290–3298, doi:10.3762/bjoc.20.273

• [54]. It was also shown by the authors that compound 18 could be efficiently converted to the fungal natural product bulgarein (5) in only two steps. Our synthesis started with the mono-iodination of 1,8-dimethoxynaphthalene (20), which was prepared in single step from the commercially available 1,8

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

• alkenes 214 (Scheme 67) [136]. Initially, I− promotes the decomposition of TBHP to generate the tert-butyloxy radical and the tert-butylperoxy radical A. The tert-butylperoxy radical A adds preferentially to the electron-deficient alkene 214 to give the electrophilic radical B, which undergoes iodination

• to generate the iodoperoxidate intermediate C. Finally, nucleophilic addition of anion of carboxylic acid to intermediate C generates the desired product 216. Based on the iodination/peroxidation strategy the approach to α-hydroxy-β-peroxyethylarenes 219 and α-alkoxy-β-peroxyethylarenes 218 from

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

• include arylation, iodination, alkynylation, thiophenolation, amination, and esterification, were carried out. Among these reactions, esterification was achieved in moderate yield under metal-free conditions by reacting the synthesized naproxen methyl ester (2-methoxyphenyl)iodonium

• , and iodination of the gemfibrozil aromatic ring by reacting them with the corresponding nucleophiles. Notably, reactions with phenol, thiophenol and benzoic acid using salts 71 in the presence of t-BuOK led to the corresponding products 72 with 61%, 69%, and 77% yields, respectively (Scheme 28). These

N-Glycosides of indigo, indirubin, and isoindigo: blue, red, and yellow sugars and their cancerostatic activity

• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 2840–2869, doi:10.3762/bjoc.20.240

• ). Dehydrogenation of the latter with DDQ afforded the anomerically pure indol-N-glycoside β-26a which upon benzylation and methylation gave products β-27a and β-27b, respectively. Iodination gave products β-28a and β-28b, however, due to the basic reaction conditions (I2, NaOH, DMF), ether rather than ester

Facile preparation of fluorine-containing 2,3-epoxypropanoates and their epoxy ring-opening reactions with various nucleophiles

• Yutaro Miyashita,
• Sae Someya,
• Tomoko Kawasaki-Takasuka,
• Tomohiro Agou and
• Takashi Yamazaki

Beilstein J. Org. Chem. 2024, 20, 2421–2433, doi:10.3762/bjoc.20.206

• nonfluorinated Rf groups which sometimes suffered from the contamination of the regioisomers as a consequence of the regiorandom attack of nucleophiles [22][23][24][25][26]. Despite such significant advantage, compound 2a was previously prepared only by 1) the LDA-mediated iodination-intramolecular ring closure

Catalysing (organo-)catalysis: Trends in the application of machine learning to enantioselective organocatalysis

• Stefan P. Schmid,
• Leon Schlosser,
• Frank Glorius and
• Kjell Jorner

Beilstein J. Org. Chem. 2024, 20, 2280–2304, doi:10.3762/bjoc.20.196

• implementations were chosen to tackle this problem. In 2022, Denmark and co-workers [132] (Figure 12) investigated a disulfonimide-catalysed atroposelective iodination with the intention of finding a general reaction procedure. After constructing an in silico library consisting of 1,478 catalysts, a universal

Metal-free double azide addition to strained alkynes of an octadehydrodibenzo[12]annulene derivative with electron-withdrawing substituents

• Naoki Takeda,
• Shuichi Akasaka,
• Susumu Kawauchi and
• Tsuyoshi Michinobu

Beilstein J. Org. Chem. 2024, 20, 2234–2241, doi:10.3762/bjoc.20.191

• 5 was prepared from phthalimide (1, Scheme 1). Iodination followed by hydrolysis afforded 4,5-diiodophthalic acid (2) in 46.7% yield. Esterification with 1-hexanol yielded compound 3 in 56.8% yield and the subsequent Sonogashira coupling with trimethylsilylacetylene provided compound 4 in 80.0

Natural resorcylic lactones derived from alternariol

• Joachim Podlech

Beilstein J. Org. Chem. 2024, 20, 2171–2207, doi:10.3762/bjoc.20.187

Chemo-enzymatic total synthesis: current approaches toward the integration of chemical and enzymatic transformations

• Ryo Tanifuji and
• Hiroki Oguri

Beilstein J. Org. Chem. 2024, 20, 1693–1712, doi:10.3762/bjoc.20.151

• utilizing the successfully overexpressed Diels–Alderase, MaDA (Scheme 5C). The chemical synthesis of 54, tri-O-acetylated precursor of the diene component 48, commenced from phenol 50. Iodination and O-acetylations of 50 followed by coupling with phosphorus ylide 51 afforded aryl iodide 52. Subsequent

• -half segment 72 was prepared from mixed anhydride 68 (Scheme 8A). Condensation with chiral auxiliary 69 and subsequent diastereoselective alkylation, followed by reductive removal of the auxiliary and iodination of the resulting primary alcohol provided alkyl iodide 70 [78]. Subsequent six-step

Tetrabutylammonium iodide-catalyzed oxidative α-azidation of β-ketocarbonyl compounds using sodium azide

• Christopher Mairhofer,
• David Naderer and
• Mario Waser

Beilstein J. Org. Chem. 2024, 20, 1510–1517, doi:10.3762/bjoc.20.135

• an ammonium hypoiodite species which first facilitates the α-iodination of the pronucleophile, followed by a phase-transfer-catalyzed nucleophilic substitution by the azide. Furthermore, we also show that an analogous α-nitration by using NaNO2 under otherwise identical conditions is possible as well

• . Based on these mechanistic details obtained so far, we were also wondering if we could get any hints concerning possible reaction intermediates. Ishihara’s group recently showed that their α-azidation protocol proceeds via in situ α-iodination first, followed by nucleophilic displacement by the azide

• first, which then facilitates the α-iodination of 1a (hereby either the formed benzoate or the hypoiodite itself may serve as a base). Intermediate 3 then undergoes a phase-transfer-catalyzed nucleophilic substitution with NaN3 thus delivering the final product 2a. With optimized conditions and a

Domino reactions of chromones with activated carbonyl compounds

• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 1256–1269, doi:10.3762/bjoc.20.108

• these products can be explained by initial formation of the corresponding 2-(salicyloyl)furans V. Iodination of the latter afforded iodonium salt W which underwent cyclization by attack of the salicylate hydroxy group to give intermediate X. Extrusion of hydrogen iodide afforded the final product

(Bio)isosteres of ortho- and meta-substituted benzenes

• H. Erik Diepers and
• Johannes C. L. Walker

Beilstein J. Org. Chem. 2024, 20, 859–890, doi:10.3762/bjoc.20.78

• 166) [64]. In addition to their synthesis of cubane 166, Coote and co-workers also reported a number of bifunctional 1,3-cubanes accessible through functional group interconversion from acid ester cubane 167 (Scheme 17D) [64]. Reduction to the alcohol (to 179) and iodination (to 180) of the carboxylic

Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

• radical recombination between C(sp3) radical 152 and the corresponding iodine-centered radical which provides iodination product 153 (Scheme 31B). It is worth noting that the iodination product is formed exclusively when using acetone as the solvent (see compound 154 in scheme C) whereas in DMF a

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments

• Aissam Okba,
• Pablo Simón Marqués,
• Kyohei Matsuo,
• Naoki Aratani,
• Hiroko Yamada,
• Gwénaël Rapenne and
• Claire Kammerer

Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30

• corresponding bis(thiophenyl) thioether, which then underwent successive bromination and iodination to give intermediate 18. Next, a two-fold Suzuki–Miyaura cross-coupling occurring chemoselectively on the iodinated positions allowed the symmetric extension of the hydrocarbon scaffold, with the insertion of two

Catalytic multi-step domino and one-pot reactions

• Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2024, 20, 254–256, doi:10.3762/bjoc.20.25

• acetaldehyde dimethyl acetal as a masked form of acetaldehyde, which is hydrolyzed in situ, allowing for a higher product yield and fewer byproducts [15]. The group of Müller describes an elegant consecutive four-component reaction involving an alkynylation–cyclization–iodination–alkylation sequence toward

Copper-promoted C5-selective bromination of 8-aminoquinoline amides with alkyl bromides

• Changdong Shao,
• Chen Ma,
• Li Li,
• Jingyi Liu,
• Yanan Shen,
• Chen Chen,
• Qionglin Yang,
• Tianyi Xu,
• Zhengsong Hu,
• Yuhe Kan and
• Tingting Zhang

Beilstein J. Org. Chem. 2024, 20, 155–161, doi:10.3762/bjoc.20.14

• chlorination and iodination reactions using ethyl chlorodifluoroacetate (6) and 1-iodobutane (8) as the respective halogenation reagents. However, these attempts ended in failure (Scheme 4, reactions 2 and 3). Furthermore, to demonstrate the synthetic usefulness of the protocol for industrial production, a

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

• groundbreaking work of Shang and Fu on photocatalytic decarboxylative alkylations in 2019, a wide range of organic transformations, such as alkylation, alkenylation, cyclization, amination, iodination, and monofluoromethylation, have been progressively achieved using a combination of iodide and PPh3. In this

• transformations such as alkenylation, alkylation, cyclization, amination, iodination, and many others. The discovery of these conversions has significantly expanded the scope and versatility of the NaI/PPh3 catalytic system, now making it a powerful tool in synthesis. Alkenylation In 2020, Shang, Fu, and

• nitroarenes 48 (Scheme 22). The protocol demonstrated excellent tolerance towards a wide range of reducible functional groups, including halogens (such as chlorine, bromine, and even iodine), aldehydes, ketones, carboxyl groups, and cyano groups. Iodination Alkyl iodide is considered to be the most reactive

Consecutive four-component synthesis of trisubstituted 3-iodoindoles by an alkynylation–cyclization–iodination–alkylation sequence

• Nadia Ledermann,
• Alae-Eddine Moubsit and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2023, 19, 1379–1385, doi:10.3762/bjoc.19.99

• generated by a consecutive four-component reaction starting from ortho-haloanilines, terminal alkynes, N-iodosuccinimide, and alkyl halides in yields of 11–69%. Initiated by a copper-free alkynylation, followed by a base-catalyzed cyclizive indole formation, electrophilic iodination, and finally

• state, in good yield. Keywords: alkynylation; catalysis; cyclization; indoles; iodination; multicomponent reactions; Introduction Indoles and their derived substitution patterns are omnipresent heterocyclic structural motifs in nature [1], many natural products [2][3], drugs [4][5][6][7][8], and dyes

• synthesis of 1,2,5-trisubstituted 7-azaindoles [34]. Inspired by the coupling–cyclization–alkylation sequence and the stepwise Sonogashira coupling–cyclization–iodination protocol to give valuable 3-iodoindoles by Amjad and Knight [35], we reasoned that the interception by an electrophilic iodination step

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

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

• -dicarbonyl compounds are treated with (diacetoxyiodo)benzene and tetrabutylammonium iodide, iodination occurs at the α-position of the nitro group, and the subsequent O-attack of the enol moiety leads to 2,3-dihydrofuran. Cyclopropane was successfully synthesized through C-attack as the acyl group became

• addition of the 1,3-dicarbonyl compound 3 to nitrostyrene 2 and the α-iodination of the adduct 4, two cyclization modes became possible owing to the ambident property of enol 12. Dihydrofuran 8 was formed in the case of an O-attack, and nitrocyclopropane 1 was formed in the case of a C-attack. Furthermore

Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities

• Jorge de Lima Neto and
• Paulo Henrique Menezes

Beilstein J. Org. Chem. 2023, 19, 399–427, doi:10.3762/bjoc.19.31

• ] between halide 37 and phenol 38 leading to the formation of diaryl ether 39, which was subjected to a regioselective iodination reaction to give compound 40. Conversion of the nitrile in compound 40 into the corresponding aldehyde 41 followed by Z-selective Still–Gennari olefination gave the cis α,β