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

• formed. The use of a chiral aryl iodide was tested, which gave products with low enantiomeric excess. However, these preliminary trials represent the first example of a catalytic, enantioselective HVI-mediated fluorocyclisation. The authors proposed a mechanism (Scheme 4) for this reaction that involved

• iodoarene difluoride 10 being generated from iodosylarene 9 (ArI=O) and HF, with iodosylarene itself generated by aryl iodide and m-CPBA. Ligand exchange of iodoarene difluoride with nitrogen and reaction with the alkene forms aziridinium intermediate A which, after nucleophilic attack by fluoride, forms

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

• formation of the Nu–Ar product and aryl iodide [21]. Second, the arylation can take place in the presence of a metal catalyst via oxidative addition, followed by reduction elimination [48][49]. Thirdly, it proceeds through a ligand-coupled arylation which involves a five-membered transition state to yield

• 62. Acetonitrile was identified as a suitable solvent for this reaction, resulting in moderate to good yields of the products. The three main steps in the reaction were oxidation of the aryl iodide, addition of the TMP auxiliary, and C–O coupling reaction. Olofsson et al. worked towards the synthesis

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

Generation of alkyl and acyl radicals by visible-light photoredox catalysis: direct activation of C–O bonds in organic transformations

• Mithu Roy,
• Bitan Sardar,
• Itu Mallick and
• Dipankar Srimani

Beilstein J. Org. Chem. 2024, 20, 1348–1375, doi:10.3762/bjoc.20.119

• electron density, which facilitates a π–π interactions with the aryl iodide system and ultimately results in the production of an electron donor–acceptor (EDA) complex 21. Photoexcitation of this EDA complex furnishes an aryl iodide radical anion and a radical cation complex 22. Then, the elimination of

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

• the presence of Ni(dme)Cl2 (a nickel(II) chloride ethylene glycol dimethyl ether complex), dtbbpy (4,4-di-tert-butyl-2,2-dipyridyl), Zn(0) and ZnI2 in DMF at 120 °C [42] (Scheme 22). The nickel catalyst catalyzed the oxidative addition and CO insertion on aryl iodide compounds, while the Zn/ZnI2

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

• ). Notably, the protocol was also applicable to 4-iodotoluene as a moderately deactivated aryl iodide and the C(sp2)–I bond cleavage occurred chemoselectively in the presence of a C(sp2)–Br bond. N-Methylpyrrole and various other substituted pyrroles could be applied as trapping agents for electron-poor aryl

Construction of hexabenzocoronene-based chiral nanographenes

• Ranran Li,
• Di Wang,
• Shengtao Li and
• Peng An

Beilstein J. Org. Chem. 2023, 19, 736–751, doi:10.3762/bjoc.19.54

• synthesis started with the preparation of the distorted HBC analogue 49, bearing an aryl iodide for the subsequent Sonogashira cross-coupling reaction with alkyne 50 to give 51. The precursor 116 containing three pre-existing HBCs was synthesized through Co-catalyzed cyclotrimerization of compound 51

Strategies in the synthesis of dibenzo[b,f]heteropines

• David I. H. Maier,
• Barend C. B. Bezuidenhoudt and
• Charlene Marais

Beilstein J. Org. Chem. 2023, 19, 700–718, doi:10.3762/bjoc.19.51

• ] reported the synthesis of substituted dibenzo[b,f]azepines 110 as unexpected products during their investigation of the Catellani reaction. The Pd-catalysed reaction of an aryl iodide 106, bromoaniline 107, norbornadiene (108) and base resulted in the norbornene-azepine intermediate 109. Heating to 130 °C

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

• active Cu(I) catalyst. The reaction was broadly successful with the steric and electronic nature of the aryl iodide having little effect on the reaction. Iron-catalyzed reactions Being the most earth-abundant d-block element, as well as orders of magnitude less expensive than other transition-metal

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• following example of styrene diamination by a chiral aryl iodide, the higher efficiency of the proposed catalyst compared to simpler aryl iodides was attributed to the additional stabilization of the I(III) intermediate by chelation via n–σ* interactions and hydrogen bonding [147] (Scheme 33). The

• enantioselective hydroxylation of benzylic positions was achieved using a chiral aryl iodide mediator [148] (Scheme 34). At the first stage, under the action of m-CPBA and sodium bromide an active form of the catalyst ArI3-Br is formed, in which the iodine–bromine bond is cleaved homolytically under visible light

• chiral copper complex. An extraordinary example of an asymmetric difluorination of alkenes with the migration of aryl or methyl groups was shown using a chiral aryl iodide catalyst [149][150] (Scheme 35). Depending on the nature of the migrating group, two mechanisms are possible that determine the

A new route for the synthesis of 1-deazaguanine and 1-deazahypoxanthine

• Raphael Bereiter,
• Marco Oberlechner and
• Ronald Micura

Beilstein J. Org. Chem. 2022, 18, 1617–1624, doi:10.3762/bjoc.18.172

• intermediates. Here, we present a new tactic for the syntheses of 1-deazaguanine and 1-deazahypoxanthine stimulated by a recently published route of our research group for the corresponding nucleosides [16][17], employing the same key reaction, namely the copper-catalyzed coupling of an aryl iodide with benzyl

• be easily prepared from its commercially available 6-chloro derivative [16]. To enable C–O coupling with benzyl alcohol, protection of the N9 with a tetrahydropyranyl group was necessary due to limited solubility of the aryl iodide. Therefore, 6-iodo-1-deazapurine was treated with tosylic acid and

Simple synthesis of multi-halogenated alkenes from 2-bromo-2-chloro-1,1,1-trifluoroethane (halothane)

• Yukiko Karuo,
• Atsushi Tarui,
• Kazuyuki Sato,
• Kentaro Kawai and
• Masaaki Omote

Beilstein J. Org. Chem. 2022, 18, 1567–1574, doi:10.3762/bjoc.18.167

• 2n was 32% (Table 2, entry 13). In the case of aminophenol (3o), nucleophilic addition occurred predominantly at the phenoxide position and the product was obtained in moderate yield (Table 2, entry 14). An aryl iodide also participated in the reaction (Table 2, entry 15). We propose the reaction

Palladium-catalyzed solid-state borylation of aryl halides using mechanochemistry

• Koji Kubota,
• Emiru Baba,
• Tamae Seo,
• Tatsuo Ishiyama and
• Hajime Ito

Beilstein J. Org. Chem. 2022, 18, 855–862, doi:10.3762/bjoc.18.86

• yields are shown. The NMR yields are shown in parentheses. Reactions of solid aryl iodide and chloride. Reaction conditions: a mixture of 1 (0.30 mmol), 2 (0.36 mmol), KOAc (0.9 mmol), Pd(OAc)2 (0.006 mmol), t-Bu3·HBF4 (0.009 mmol), and H2O (60 μL) was milled in a 1.5 mL stainless-steel jar at 30 Hz

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions

• Surendran Amrutha,
• Sankaran Radhika and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 262–285, doi:10.3762/bjoc.18.31

• with XPhoS provided only 12% of the product. Both, Fe and Pd are essentially required for the successive coupling in nanocomposites, and hence iron composition plays a major role in the activity of the nanoparticles. Selective reaction between an aryl iodide/bromide with the terminal alkyne was facile

• lower in case of an ortho-substituted aryl iodide than the yields obtained from meta- and para-substituted aryl iodides. Kumar et al. reported a ferromagnetic α-Fe2O3-catalyzed coupling of phenylacetylene with aryl iodides (Scheme 12) [29]. They synthesized an azaindole-appended hexaphenylbenzene (HPB

• substituents like iodo, fluoro, methyl, acetyl, and methoxy groups. The yield of the coupling product was observed to be decreased when the steric demand of aryl iodide species increased as in the case of the naphthyl-substituted iodo derivative. An efficient method for the synthesis of 7-azaindole ring

Photoredox catalysis in nickel-catalyzed C–H functionalization

• Lusina Mantry,
• Rajaram Maayuri,
• Vikash Kumar and
• Parthasarathy Gandeepan

Beilstein J. Org. Chem. 2021, 17, 2209–2259, doi:10.3762/bjoc.17.143

• )‒H arylation as shown in Figure 3 [55]. Thus, the in situ-generated nickel(0) 3-IV undergoes an oxidative addition with the aryl iodide 2 to form the nickel(II)–aryl complex 3-V. The photoredox-generated nucleophilic α-amino radical 3-VIII readily combines with the nickel(II) species 3-V to generate

A recent overview on the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles

• Pezhman Shiri,
• Ali Mohammad Amani and
• Thomas Mayer-Gall

Beilstein J. Org. Chem. 2021, 17, 1600–1628, doi:10.3762/bjoc.17.114

• bond functionalization reaction sequence with triazole-bearing aryl iodide 140, catalyzed by alloy-structured Pd/Cu bimetallic nanoparticles stabilized by a binaphthyl moiety, Pd/Cu-BNP 139. The Pd/Cu-BNP nanoparticles 139 were demonstrated to be an efficient and recyclable catalyst, and triazoles

Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent

• Tatsuhiro Uchikura,
• Nanami Kamiyama,
• Taisuke Ishikawa and
• Takahiko Akiyama

Beilstein J. Org. Chem. 2020, 16, 2442–2447, doi:10.3762/bjoc.16.198

• (I)–CF3 species, generated through the reaction of benzimidazoline 2 with CuI under basic conditions, underwent an oxidative addition reaction with the aryl iodide to generate a Cu(III) complex. A subsequent reductive elimination furnished the trifluoromethylarene and Cu(I). Because an electron

• synthesis. Experimental General procedure of trifluoromethylation: Aryl iodide 1 (0.1 mmol), 2 (56 mg, 0.2 mmol), CuI (3.8 mg, 0.02 mmol), 2,2’-bipyridyl (12.5 mg, 0.08 mmol), and potassium carbonate (55.6 mg, 0.4 mmol) were mixed in benzonitrile (1.0 mL), and the mixture heated to 90 °C. After 48 h

Palladium-catalyzed regio- and stereoselective synthesis of aryl and 3-indolyl-substituted 4-methylene-3,4-dihydroisoquinolin-1(2H)-ones

• Valeria Nori,
• Antonio Arcadi,
• Armando Carlone,
• Fabio Marinelli and
• Marco Chiarini

Beilstein J. Org. Chem. 2020, 16, 1084–1091, doi:10.3762/bjoc.16.95

• (Te), Italy 10.3762/bjoc.16.95 Abstract Cascade cyclocarbopalladation of the readily available aryl/alkyl-substituted propargylic amides containing an aryl iodide moiety, followed by Suzuki–Miyaura coupling with arylboronic acids, allowed an efficient regio- and stereoselective synthesis of

Synthesis and anticancer activity of bis(2-arylimidazo[1,2-a]pyridin-3-yl) selenides and diselenides: the copper-catalyzed tandem C–H selenation of 2-arylimidazo[1,2-a]pyridine with selenium

• Mio Matsumura,
• Tsutomu Takahashi,
• Hikari Yamauchi,
• Shunsuke Sakuma,
• Yukako Hayashi,
• Tadashi Hyodo,
• Tohru Obata,
• Kentaro Yamaguchi,
• Yasuyuki Fujiwara and
• Shuji Yasuike

Beilstein J. Org. Chem. 2020, 16, 1075–1083, doi:10.3762/bjoc.16.94

• -phenanthroline catalytic system [28]. Guo, Han, et al. reported a method that used a Cu(OAc)2/1,10-phenanthroline catalyst in the presence of KOH (2 equiv); this method replaced the aryl source from an arylboronic acid with an aryl iodide [30]. Zhou et al. reported the reactions of imidazopyridines, Se powder

Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas

• Zhenghui Liu,
• Peng Wang,
• Zhenzhong Yan,
• Suqing Chen,
• Dongkun Yu,
• Xinhui Zhao and
• Tiancheng Mu

Beilstein J. Org. Chem. 2020, 16, 645–656, doi:10.3762/bjoc.16.61

• lower yields (21 61% and 22 60%). Also, iodobenzenes with an acetyl group in either ortho, meta, or para-position gave the products in satisfactory yields (23 79%, 24 81% and 25 87%). 1-Iodo-3,4-methylenedioxybenzene performed well providing aldehyde 26 with 92% yield. Aryl iodide with an acetamido

• corresponding aldehydes 36–42 were isolated with yields of 65−73%. Isotope labeling experiments Isotope labeling experiments were conducted to study the mechanism of the reductive carbonylation of aryl iodide with CO and H2 under our optimized conditions, using 13CO and D2 instead of CO and H2, respectively, as

• ]. First, RhCl3·3H2O reacted with PPh3 to form Rh(PPh3)3Cl (A), followed by an oxidative addition of Rh(PPh3)3Cl (A) to the aryl iodide, producing the corresponding arylrhodium complex (B). Then, the coordination and insertion of CO led to the formation of benzoylrhodium complex (C). Next, metathesis with

Recent advances in photocatalyzed reactions using well-defined copper(I) complexes

• Mingbing Zhong,
• Xavier Pannecoucke,
• Philippe Jubault and
• Thomas Poisson

Beilstein J. Org. Chem. 2020, 16, 451–481, doi:10.3762/bjoc.16.42

• corresponding aryl iodide. The aryl radical can then add to the allylating reagent, which, after tosyl radical elimination, provides the desired product. Finally, the active catalyst is regenerated thanks to the use of DIPEA as a sacrificial reductant. Note that this reaction was inefficient with aryl iodides

• , based on their findings, suggested the following mechanism: After irradiation under blue light, the excited [Cu(I)]* complex is reduced by the organic base DIPEA to produce a [Cu(0)] complex. The latter undergoes an SET with the aryl iodide to generate the radical anion from aryl iodide, which collapses

• moderate to good yields, and the functional group tolerance was excellent. Later in 2018, Evano and co-workers used their methodology to reduce aryl iodide for the synthesis of the alkaloids rosettacin, luotonin A, and deoxyvasicinone (Scheme 22) [37]. The developed strategy relied on the addition of an

Room-temperature Pd/Ag direct arylation enabled by a radical pathway

• Amy L. Mayhugh and
• Christine K. Luscombe

Beilstein J. Org. Chem. 2020, 16, 384–390, doi:10.3762/bjoc.16.36

• cycle. This type of mechanism has been previously proposed for aryl and alkene alkylations [27][28], but not for direct arylation systems. A possible mechanism is outlined in Scheme 3, informed by the previous reports [27][28][29][30]. The aryl iodide 4 undergoes SET with an excited palladium(0) species

Palladium-catalyzed Sonogashira coupling reactions in γ-valerolactone-based ionic liquids

• László Orha,
• József M. Tukacs,
• László Kollár and
• László T. Mika

Beilstein J. Org. Chem. 2019, 15, 2907–2913, doi:10.3762/bjoc.15.284

• catalytic system could be applied to various iodoarene substrates and the substrate reactivity was not influenced dramatically by the electronic parameters of the substituents. Both electron-withdrawing (chloro, fluoro and bromo) and electron-donating (methyl, methoxy) groups were tolerated on the aryl

• iodide (Table 3, entries 2–7). Under identical conditions, 2-iodothiophene, and iodopyridine derivatives could also easily be converted to the corresponding acetylene with good or even excellent isolated yields (3i–n). When 2-amino-3-iodopyridine (1i) was converted no C–N bond formation was detected

Thermal stability of N-heterocycle-stabilized iodanes – a systematic investigation

• Andreas Boelke,
• Yulia A. Vlasenko,
• Mekhman S. Yusubov,
• Boris J. Nachtsheim and
• Pavel S. Postnikov

Beilstein J. Org. Chem. 2019, 15, 2311–2318, doi:10.3762/bjoc.15.223

• cyclic (33) diaryliodonium salt. Pseudocyclic salt 25 was heated to 185 °C and the resulting oily residue was analyzed by GC–MS (Scheme 1a). Besides dearylation to aryl iodide 25a we observed the formation of an N-arylated product 25b in significant amounts. In a similar experiment compound 33 was heated

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165