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

• renders them particularly suitable for the generation of arynes for subsequent use in a wide range of synthetic applications. The common approach to generate cyclic biaryl λ3-bromanes is based on thermal decomposition of hazardous diazonium salts. Herein, we disclose a mild and straightforward approach to

• ; electrochemistry; hypervalent bromine; Introduction Chemistry of hypervalent bromine(III) species has experienced rapid advancements during the recent years [1][2]. The remarkable nucleofugality of aryl bromides in hypervalent bromine(III) compounds has been exploited in the generation of arynes from cyclic

• diaryl λ3-bromanes under remarkably mild conditions with subsequent applications of the in situ-generated arynes in cycloaddition reactions [3], meta-selective reactions with oxygen and nitrogen nucleophiles [4][5], regiodivergent meta or ortho-alkynylations [6], and regioselective (di)halogenation [7

Cu(OTf)₂-catalyzed multicomponent reactions

• Sara Colombo,
• Camilla Loro,
• Egle M. Beccalli,
• Gianluigi Broggini and
• Marta Papis

Beilstein J. Org. Chem. 2025, 21, 122–145, doi:10.3762/bjoc.21.7

• these conditions the reaction between aryl thiosulfonates with arynes to give sulfones is competitive. Cu(OTf)2 is essential to remove the sulfinate anions in the reaction medium, avoiding side reactions arising from their attack to the electrophilic arynes. The so-obtained products are susceptible of

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

• underscored by the successful conversion of various α,α-difluoromethyl ketone groups into corresponding esters, amides, and difluoromethyl groups [58]. In 2021, Nilova and colleagues outlined an approach for the synthesis of highly hindered 1,2,3,4-tetrasubstituted benzenoid rings 15 using arynes generated

Biphenylene-containing polycyclic conjugated compounds

• Cagatay Dengiz

Beilstein J. Org. Chem. 2023, 19, 1895–1911, doi:10.3762/bjoc.19.141

• approaches have gained popularity for synthesizing biphenylene derivatives [23]. The utilization of in-situ aryne synthesis to generate biphenylene through the dimerization of arynes 2 from diverse substrates has gained popularity. However, this approach occasionally gives rise to the production of high

• -catalyzed formal [2 + 2] cycloaddition reactions but also the emergence of tetracene trimer 86 and tetramer 88 stemming from [2 + 2 + 2] cycloaddition reactions (Scheme 18). It is proposed that an aryne intermediate is formed after thermal activation and that the observed end products are formed from arynes

Visible-light-mediated copper photocatalysis for organic syntheses

• Yajing Zhang,
• Qian Wang,
• Zongsheng Yan,
• Donglai Ma and
• Yuguang Zheng

Beilstein J. Org. Chem. 2021, 17, 2520–2542, doi:10.3762/bjoc.17.169

• undergoes radical addition with the N-substituted maleimide (Scheme 25). In 2017, Wu and co-workers [94] reported the α-amino C−H functionalization of aromatic amines 51 with nucleophiles, including arynes or aromatic olefins 52, indoles, acyclic β-ketoester 53, and β-diketone 54 (Scheme 26). Mechanistic

Transition-metal-free intramolecular Friedel–Crafts reaction by alkene activation: A method for the synthesis of some novel xanthene derivatives

• Tülay Yıldız,
• İrem Baştaş and
• Hatice Başpınar Küçük

Beilstein J. Org. Chem. 2021, 17, 2203–2208, doi:10.3762/bjoc.17.142

• intramolecular coupling of arynes by aldehydes or phenols [21][22][23][24], and Lewis acid-catalyzed cyclization of salicylaldehydes and cyclohexenones or tetralones [25]. Some other new and prominent synthesis methods of xanthenes are the tandem arylation/Friedel–Crafts reaction of o-hydroxy bisbenzylic

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

A straightforward conversion of 1,4-quinones into polycyclic pyrazoles via [3 + 2]-cycloaddition with fluorinated nitrile imines

• Greta Utecht-Jarzyńska,
• Karolina Nagła,
• Grzegorz Mlostoń,
• Heinz Heimgartner,
• Marcin Palusiak and
• Marcin Jasiński

Beilstein J. Org. Chem. 2021, 17, 1509–1517, doi:10.3762/bjoc.17.108

• respective hydrazonoyl bromides 8 and smoothly undergo [3 + 2]-cycloadditions with both electron-rich C=C dipolarophiles [27][28][29] and arynes [30], yielding the corresponding pyrazole derivatives. Unexpectedly, they reacted also with electron-deficient polyfluorinated thioamides to give the desired 1,3,4

Photocatalyzed syntheses of phenanthrenes and their aza-analogues. A review

• Alessandra Del Tito,
• Havall Othman Abdulla,
• Davide Ravelli,
• Stefano Protti and
• Maurizio Fagnoni

Beilstein J. Org. Chem. 2020, 16, 1476–1488, doi:10.3762/bjoc.16.123

• the design of dye-sensitized solar cells (DSSC) [4]. Typical methods for the construction of a phenanthrene core involve transition-metal-catalyzed cycloisomerizations starting from arynes [5][6], o-alkynyl-biaryls [7][8], or substituted N-tosylhydrazones [9]. However, since the introduction in 1964

• Pd(OAc)2 (5 mol %), was involved in the design of an efficient annulation between benzamides and in situ-generated arynes. The process occurred under oxygen saturated atmosphere at room temperature, likewise offering a straightforward access to the phenanthridone backbone [93]. Conclusion

Formation of an unexpected 3,3-diphenyl-3H-indazole through a facile intramolecular [2 + 3] cycloaddition of the diazo intermediate

• Andrew T. King,
• Hugh G. Hiscocks,
• Lidia Matesic,
• Mohan Bhadbhade,
• Roger Bishop and
• Alison T. Ung

Beilstein J. Org. Chem. 2019, 15, 1347–1354, doi:10.3762/bjoc.15.134

• ]. More recently, the formation of cyclic 3,3-disubstituted 3H-indazoles was reported to form mainly through the [2 + 3] cycloaddition of diazo compounds with arynes under mild reaction conditions [29][30][31]. However, none of these contained a 2-diphenylmethyl (benzhydryl) aniline system, as found in

[3 + 2]-Cycloaddition reaction of sydnones with alkynes

• Veronika Hladíková,
• Jiří Váňa and
• Jiří Hanusek

Beilstein J. Org. Chem. 2018, 14, 1317–1348, doi:10.3762/bjoc.14.113

• -bistriflates) with two different dipoles from which one was 3-phenyl-4-(4-methoxyphenyl)sydnone (Scheme 14). The reason for the much better regioselectivity probably lies in the steric hindrance between the bulky t-BuMe2Si and 4-MeO-Ph groups. The in situ generation of arynes or six-membered cycloalkynes from

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

Preparation and isolation of isobenzofuran

• Morten K. Peters and
• Rainer Herges

Beilstein J. Org. Chem. 2017, 13, 2659–2662, doi:10.3762/bjoc.13.263

• synthetic application is probably the preparation of annulated polycyclic aromatic hydrocarbons by cycloaddition to arynes [8][12]. However, the high reactivity of isobenzofurans comes at the cost of low stability [13]. 1,3-Diphenylisobenzofuran is reasonably stable and commercially available and therefore

Asymmetric synthesis of quaternary aryl amino acid derivatives via a three-component aryne coupling reaction

• Elizabeth P. Jones,
• Peter Jones,
• Andrew J. P. White and
• Anthony G. M. Barrett

Beilstein J. Org. Chem. 2011, 7, 1570–1576, doi:10.3762/bjoc.7.185

• . Hydrolysis of the sterically less hindered adducts gave the corresponding quaternary amino acids with no racemization, whereas hydrolytic ring opening gave the corresponding valine dipeptides from bulkier bislactims. Keywords: aryl amino acids; arynes; asymmetric; multicomponent; quaternary; Introduction

• Arynes are exceptionally versatile reactive intermediates in organic synthesis. Not only are they able to participate in cycloaddition reactions, they also readily undergo addition reactions with nucleophiles, and the resultant aryl anions may be protonated or undergo alternative transformations [1][2][3

• ][4][5][6]. We are particularly interested in the use of arynes in multicomponent coupling reactions, in which the resultant aryl carbanion following nucleophilic attack is allowed to react with a further electrophile, providing ortho-disubstituted, functionalized aromatic products in a one-pot

Bromine–lithium exchange: An efficient tool in the modular construction of biaryl ligands

• Laurence Bonnafoux,
• Frédéric R. Leroux and
• Françoise Colobert

Beilstein J. Org. Chem. 2011, 7, 1278–1287, doi:10.3762/bjoc.7.148

• ). Results and Discussion Regioselective bromine–lithium exchange on polybrominated biphenyls Our group recently reported the efficient coupling of organolithium intermediates with arynes, the so-called "ARYNE coupling" [25][31][36]. This protocol is based on the formation of a thermodynamically stable

Trifluoromethyl ethers – synthesis and properties of an unusual substituent

• Frédéric R. Leroux,
• Baptiste Manteau,
• Jean-Pierre Vors and
• Sergiy Pazenok

Beilstein J. Org. Chem. 2008, 4, No. 13, doi:10.3762/bjoc.4.13

• - and para-positions (Figure 5) [76]. By contrast, bromo(trifluoromethoxy)benzenes are metalated at −100 °C by bases such as LDA at a position next to the oxygen substituent (Scheme 18) [74]. At temperatures above −75 °C, lithium bromide elimination generates didehydro(trifluoromethoxy)benzenes ("arynes