Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides

• Kan Tang,
• Megan R. Brown,
• Chad Risko,
• Melissa K. Gish,
• Garry Rumbles,
• Phuc H. Pham,
• Oana R. Luca,
• Stephen Barlow and
• Seth R. Marder

Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142

• and photocatalysts used, and (c) schematic for the present approach, along with structures of 1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[d]imidazoles, (Y-DMBI)2, and the corresponding monomer cations, specifically the first reported in the literature and those used in this work. (a) A

Benzoimidazolium-derived dimeric and hydride n-dopants for organic electron-transport materials: impact of substitution on structures, electrochemistry, and reactivity

• Swagat K. Mohapatra,
• Khaled Al Kurdi,
• Samik Jhulki,
• Georgii Bogdanov,
• John Bacsa,
• Maxwell Conte,
• Tatiana V. Timofeeva,
• Seth R. Marder and
• Stephen Barlow

Beilstein J. Org. Chem. 2023, 19, 1651–1663, doi:10.3762/bjoc.19.121

• States National Renewable Energy Laboratory, Chemistry and Nanoscience Center, Golden, Colorado, 80401, United States 10.3762/bjoc.19.121 Abstract 1,3-Dimethyl-2,3-dihydrobenzo[d]imidazoles, 1H, and 1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[d]imidazoles, 12, are of interest as n-dopants

• increasing its ease of storage and handling. Arguably, the most widely investigated air-inert n-dopants are 1,3-dimethyl-2,3-dihydrobenzo[d]imidazoles (DMBI-H, 1H, Figure 1); these species have been known for decades (e.g., 1aH, one of the simplest such derivatives, was first reported in 1954 [6]), but were

Metal catalyst-free N-allylation/alkylation of imidazole and benzimidazole with Morita–Baylis–Hillman (MBH) alcohols and acetates

• Olfa Mhasni,
• Jalloul Bouajila and
• Farhat Rezgui

Beilstein J. Org. Chem. 2023, 19, 1251–1258, doi:10.3762/bjoc.19.93

• , such alcohols were in situ converted into the corresponding O-allyl carbamates as leaving groups, followed by their reaction with imidazoles, affording the SN2’ products 3 (Scheme 1, reaction 1, iii). Correlatively, we have previously reported a direct amination of cyclic MBH alcohols 4 with morpholine

• substitution of MBH adducts [23][24][25][26], we disclose in this work a simple and efficient procedure for the synthesis of N-substituted imidazoles 6–8. The products were obtained either through direct conversions of the corresponding cyclic MBH alcohols 4 as well as acetates 5 in the presence of imidazoles

• ). Similarly, the five-membered acetate 5b reacted under the same conditions and gave the N-allyl-substituted imidazole 6b in 65% yield (Table 1, entry 2). Furthermore, treatment of the available secondary acetates 5c,d (R = Me) with imidazoles 2a and 2b (2 equiv) in refluxing toluene afforded the N

Asymmetric tandem conjugate addition and reaction with carbocations on acylimidazole Michael acceptors

• Brigita Mudráková,
• Renata Marcia de Figueiredo,
• Jean-Marc Campagne and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 881–888, doi:10.3762/bjoc.19.65

• a tandem reaction comprising the Cu–NHC-catalyzed addition of dialkylzinc reagents to enoyl imidazoles followed by a trapping reaction with various onium compounds (Scheme 1). In this work we show the development of this methodology and its application to a range of acylimidazoles and carbocations

Synthesis and reactivity of azole-based iodazinium salts

• Thomas J. Kuczmera,
• Annalena Dietz,
• Andreas Boelke and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2023, 19, 317–324, doi:10.3762/bjoc.19.27

• . Next, the iodonium center was stabilized through an additional N-coordination via ortho-pyrazole substitution, giving the iodonium salts 5ba and 5bb in 88% and 50% yield. When replacing imidazoles by indazoles the oxidation was not as efficient giving the products 5bc and 5bd with only 24% and 44

Functionalization of imidazole N-oxide: a recent discovery in organic transformations

• Koustav Singha,
• Imran Habib and
• Mossaraf Hossain

Beilstein J. Org. Chem. 2022, 18, 1575–1588, doi:10.3762/bjoc.18.168

• –elimination pathway (SNHAE), where deoxygenation of imidazole 1-oxide resulted in the formation of perfluoroarylated 2H-imidazoles; and (B) addition–oxidation pathway (SNHAO), where without affecting the N–O bond of imidazole 1-oxides, perfluoroarylated 2H-imidazole 1-oxides were obtained as final products

• nucleophilic acylation catalyst in THF as solvent for 1 h. In this reaction, the yield for the transformation of 2-chloro-1-(4-methoxyphenyl)-4,5-dimethyl-1H-imidazole (19a) was 80% when 1.0 equiv TsCl was used. 2-Chloro-1H-imidazoles 20b,c and the corresponding brominated products 21a–c using TsBr were also

One-pot synthesis of 2-arylated and 2-alkylated benzoxazoles and benzimidazoles based on triphenylbismuth dichloride-promoted desulfurization of thioamides

• Arisu Koyanagi,
• Yuki Murata,
• Shiori Hayakawa,
• Mio Matsumura and
• Shuji Yasuike

Beilstein J. Org. Chem. 2022, 18, 1479–1487, doi:10.3762/bjoc.18.155

• , and achieved the syntheses of 2-aryl- and 2-alkylbenzazoles, such as oxazoles, imidazoles, and thiazole, in satisfactory yields. The protocol was successfully applied to the synthesis of tafamidis, a clinically used drug for transthyretin amyloid inhibition. The reaction is simple, can be performed in

Scope of tetrazolo[1,5-a]quinoxalines in CuAAC reactions for the synthesis of triazoloquinoxalines, imidazoloquinoxalines, and rhenium complexes thereof

• Laura Holzhauer,
• Chloé Liagre,
• Olaf Fuhr,
• Nicole Jung and
• Stefan Bräse

Beilstein J. Org. Chem. 2022, 18, 1088–1099, doi:10.3762/bjoc.18.111

• desired product 16 whereas addition of zinc powder seems to have different effects depending on the derivative (see Supporting Information File 1). We could then show that the conversion of tetrazoles to both triazoles and imidazoles can occur together in the same molecule. When bis(tetrazolo)[1,5-a:5',1

Cs₂CO₃-Promoted reaction of tertiary bromopropargylic alcohols and phenols in DMF: a novel approach to α-phenoxyketones

• Ol'ga G. Volostnykh,
• Olesya A. Shemyakina,
• Anton V. Stepanov and
• Igor' A. Ushakov

Beilstein J. Org. Chem. 2022, 18, 420–428, doi:10.3762/bjoc.18.44

• transformations. For example, bromoacetylenes were demonstrated to add imidazoles, imidazolines [12], and benzimidazoles [13][14] to give vinyl bromides. Sulfonamides reacted with bromoacetylenes to deliver N-bromovinyl-p-toluenesulfonamides that under Heck reaction conditions afforded N-(p-toluenesulfonyl

• )pyrroles [15]. The CsF-promoted nucleophilic addition of isocyanides to bromoacetylenes furnished the functionalized bromovinyl amides followed by Pd-catalyzed formation of 5-iminopyrrolone [16]. Sequential nucleophilic addition/intramolecular cyclization of amidine with bromoacetylenes led to imidazoles

Multi-faceted reactivity of N-fluorobenzenesulfonimide (NFSI) under mechanochemical conditions: fluorination, fluorodemethylation, sulfonylation, and amidation reactions

• José G. Hernández,
• Karen J. Ardila-Fierro,
• Dajana Barišić and
• Hervé Geneste

Beilstein J. Org. Chem. 2022, 18, 182–189, doi:10.3762/bjoc.18.20

• functionalizations [22][23]. In particular, efficient fluorination protocols are long sought after in several areas of science, including medicinal chemistry [24]. Next to fluorination, in this work, we also have investigated NFSI as a source for mechanochemical sulfonylation of imidazoles and amidation reactions

Asymmetric organocatalytic Michael addition of cyclopentane-1,2-dione to alkylidene oxindole

• Estelle Silm,
• Ivar Järving and
• Tõnis Kanger

Beilstein J. Org. Chem. 2022, 18, 167–173, doi:10.3762/bjoc.18.18

• , 2-oxobut-3-enoates [10]. A 1,2-dicarbonyl moiety is also an important structural fragment present in various natural products and biologically active compounds [11]. 1,2-Diketones have been used for the synthesis of photosensitive polymers [12] and substituted imidazoles [13][14] and have been used

One-step synthesis of imidazoles from Asmic (anisylsulfanylmethyl isocyanide)

• Louis G. Mueller,
• Allen Chao,
• Embarek AlWedi and
• Fraser F. Fleming

Beilstein J. Org. Chem. 2021, 17, 1499–1502, doi:10.3762/bjoc.17.106

• Substituted imidazoles are readily prepared by condensing the versatile isocyanide Asmic, anisylsulfanylmethylisocyanide, with nitrogenous π-electrophiles. Deprotonating Asmic with lithium hexamethyldisilazide effectively generates a potent nucleophile that efficiently intercepts nitrile and imine

• electrophiles to afford imidazoles. In situ cyclization to the imidazole is promoted by the conjugate acid, hexamethyldisilazane, which facilitates the requisite series of proton transfers. The rapid formation of imidazoles and the interchange of the anisylsulfanyl for hydrogen with Raney nickel make the method

• a valuable route to mono- and disubstituted imidazoles. Keywords: Asmic; cyclization; imidazoles; isocyanides; nitriles; Introduction The imidazole core is the seventh most prevalent heterocycle among nitrogen-containing pharmaceuticals [1]. The privileged efficacy of imidazoles emanates from the

Synthesis of β-triazolylenones via metal-free desulfonylative alkylation of N-tosyl-1,2,3-triazoles

• Soumyaranjan Pati,
• Renata G. Almeida,
• Eufrânio N. da Silva Júnior and
• Irishi N. N. Namboothiri

Beilstein J. Org. Chem. 2021, 17, 762–770, doi:10.3762/bjoc.17.66

• precursors in denitrogenative transannulation reactions under metal-catalysed conditions to form other heterocycles such as functionalized pyrroles, imidazoles and pyridines (Scheme 1b) [11][12][13]. The traditional method for the synthesis of triazole unit is the Huisgen 1,3-dipolar cycloaddition between

Synthesis of N-perfluoroalkyl-3,4-disubstituted pyrroles by rhodium-catalyzed transannulation of N-fluoroalkyl-1,2,3-triazoles with terminal alkynes

• Olga Bakhanovich,
• Viktor Khutorianskyi,
• Vladimir Motornov and
• Petr Beier

Beilstein J. Org. Chem. 2021, 17, 504–510, doi:10.3762/bjoc.17.44

• -sulfonyl-1,2,3-triazoles (Scheme 1) [11][12][13][14][15][16][17]. We have recently reported that N-perfluoroalkyl-1,2,3-triazoles [18] undergo rhodium-catalyzed transannulation reactions leading to various nitrogen heterocycles, such as imidazoles, pyrrolones, imidazolones, oxazoles, azepines [19][20][21

Synthesis of purines and adenines containing the hexafluoroisopropyl group

• Viacheslav Petrov,
• Rebecca J. Dooley,
• Alexander A. Marchione,
• Elizabeth L. Diaz,
• Brittany S. Clem and
• William Marshall

Beilstein J. Org. Chem. 2020, 16, 2739–2748, doi:10.3762/bjoc.16.224

• for the introduction of a hexafluoroisopropyl group based on the reaction of tetrakis(trifluoromethyl)-1,3-dithietane (1) with the corresponding azoles [17]. Since this methodology is simple and works for a wide variety of imidazoles, including benzimidazole, we decided to explore the applicability of

• this method to the modification of biologically active imidazoles, such as adenine and purine derivatives. The results of this study are reported in this article. Results and Discussion Despite the presence of two electron-withdrawing nitrogen atoms in the aromatic ring, purine (2) was found to react

Nocarimidazoles C and D, antimicrobial alkanoylimidazoles from a coral-derived actinomycete Kocuria sp.: application of ¹J_C,H coupling constants for the unequivocal determination of substituted imidazoles and stereochemical diversity of anteisoalkyl chains in microbial metabolites

• Md. Rokon Ul Karim,
• Enjuro Harunari,
• Amit Raj Sharma,
• Naoya Oku,
• Kazuaki Akasaka,
• Daisuke Urabe,
• Mada Triandala Sibero and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2020, 16, 2719–2727, doi:10.3762/bjoc.16.222

• those of synthetically prepared model imidazoles. The absolute configurations of the anteisoalkanoyl group present in 1, 4, and 5 were determined by low-temperature HPLC analysis of the degradation products labeled with a chiral anthracene reagent, which revealed that 1 is a mixture of the R- and S

• 1 and 4 exhibited weak cytotoxicity against P388 murine leukemia cells, with an IC50 of 38 and 33 μM, respectively. Conclusion Alkanoylimidazoles, 4-acylated imidazoles of varying chain length and terminal branching, with occasional substitution at C-5 by an amino group, are an emerging class of

Access to highly substituted oxazoles by the reaction of α-azidochalcone with potassium thiocyanate

• Mysore Bhyrappa Harisha,
• Pandi Dhanalakshmi,
• Rajendran Suresh,
• Raju Ranjith Kumar and
• Shanmugam Muthusubramanian

Beilstein J. Org. Chem. 2020, 16, 2108–2118, doi:10.3762/bjoc.16.178

• precursor for nitrogen heterocycles. As a part of our synthetic design towards the construction of five-membered heterocycles, we have previously reported the synthesis of highly substituted imidazoles [6], indoles [7] and pyrroles [8] starting from different azidochalcones. In continuation, employing α

• have reported the TMSOTf-catalyzed synthesis of highly substituted imidazoles from α-azidochalcones under mild conditions [65]. As a sequel, the synthesis of oxazoles with an arylimino substituent has been accomplished in this work. The biologically important arylimino group [66][67][68][69] integrated

Regiodivergent synthesis of functionalized pyrimidines and imidazoles through phenacyl azides in deep eutectic solvents

• Paola Vitale,
• Luciana Cicco,
• Ilaria Cellamare,
• Filippo M. Perna,
• Antonio Salomone and
• Vito Capriati

Beilstein J. Org. Chem. 2020, 16, 1915–1923, doi:10.3762/bjoc.16.158

• °C) in the presence or absence of bases (Et3N). Keywords: deep eutectic solvents; imidazoles; phenacyl azides; phenacyl halides; pyrimidines; Introduction In a world with dwindling petroleum resources, the setting up of more and more sustainable routes for the preparation of heterocyclic compounds

• place smoothly using such neoteric solvents (Scheme 1, path a) [16]. Among nitrogen-containing heterocyles, imidazoles and pyrimidines are important structural scaffolds commonly found in natural products [17][18], light-emitting devices [19][20], and pharmacologically active compounds as anticancer

• chloride (1b) with NaN3 (1.5 equiv) in ChCl/Gly at 80 °C gave the best results, as it provided the adducts 3a/3a' in an overall 88% yield after 12 h reaction time (Table 1, entries 1–4). Of note, imidazoles 3a/3a' were found to precipitate directly from the aforementioned eutectic mixture during the

Natural dolomitic limestone-catalyzed synthesis of benzimidazoles, dihydropyrimidinones, and highly substituted pyridines under ultrasound irradiation

• Kumar Godugu,
• Venkata Divya Sri Yadala,
• Mohammad Khaja Mohinuddin Pinjari,
• Trivikram Reddy Gundala,
• Lakshmi Reddy Sanapareddy and
• Chinna Gangi Reddy Nallagondu

Beilstein J. Org. Chem. 2020, 16, 1881–1900, doi:10.3762/bjoc.16.156

• . Conclusion An environmentally benign NDL catalyst was characterized and utilized as a heterogeneous catalyst for the synthesis of 2-aryl-1-arylmethyl-1H-benzo[d]imidazoles, dihydropyrimidinones/ -thiones, and 2-amino-4-(hetero)aryl-3,5-dicarbonitrile-6-sulfanylpyridines in a mixture of ethanol and H2O 1:1

• conditions.a Effect of the catalyst loading.a Effect of the temperature.a NDL-catalyzed synthesis of 2-aryl-1-arylmethyl-1H-benzo[d]imidazoles 3.a NDL-catalyzed synthesis of dihydropyrimidinone/-thione derivatives 7.a NDL-catalyzed synthesis of 2-amino-4-(hetero)aryl-3,5-dicarbonitrile-6-sulfanylpyridines 11.a

• Green chemistry metrics for the synthesis of 2-aryl-1-arylmethyl-1H-benzo[d]imidazoles 3. Green chemistry metrics for the synthesis of dihydropyrimidinones/-thiones 7. Green chemistry metrics for the synthesis of 2-amino-4-(hetero)aryl-3,5-dicarbonitrile-6-sulfanylpyridines 11. Supporting Information

Architecture and synthesis of P,N-heterocyclic phosphine ligands

• Wisdom A. Munzeiwa,
• Bernard Omondi and
• Vincent O. Nyamori

Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35

• deprotection then furnished 83b in reasonable yields between 68 and 87%. Bis(diphenylphosphine)-substituted imidazoles were also synthesized by Karthik et al. [87] starting from the diiodoimidazole derivative 84. The lithium chloride mediated magnesium/iodine exchange reaction of 84 followed by the addition of

Reversible switching of arylazopyrazole within a metal–organic cage

• Anton I. Hanopolskyi,
• Soumen De,
• Michał J. Białek,
• Yael Diskin-Posner,
• Liat Avram,
• Moran Feller and
• Rafal Klajn

Beilstein J. Org. Chem. 2019, 15, 2398–2407, doi:10.3762/bjoc.15.232

• imidazoles are denoted by black arrows. Color codes: C, gray; N, blue; Pd, orange. Hydrogens, counterions, and solvent molecules are not shown for clarity. UV–vis absorption spectrum of an aqueous solution of (E-1)22 (blue) and following exposure of this solution to UV light for 5 min (orange). Inset: Ten

1,2,3-Triazolium macrocycles in supramolecular chemistry

• Mastaneh Safarnejad Shad,
• Pulikkal Veettil Santhini and
• Wim Dehaen

Beilstein J. Org. Chem. 2019, 15, 2142–2155, doi:10.3762/bjoc.15.211

• imidazoles [8][9], polypyrroles [10][11], and indole moieties [12][13], as part of supramolecular receptors, triazole heterocycles containing macrocycles have recently been introduced as new host molecules for the selective recognition of ions, mechanically interlocked molecules (MIMs), supramolecular

1,2,3,4-Tetrahydro-1,4,5,8-tetraazaanthracene revisited: properties and structural evidence of aromaticity loss

• Arnault Heynderickx,
• Sébastien Nénon,
• Olivier Siri,
• Vladimir Lokshin and
• Vladimir Khodorkovsky

Beilstein J. Org. Chem. 2019, 15, 2059–2068, doi:10.3762/bjoc.15.203

• hydroquinones or chloranilic acid as the H-bond donors (the O–H···N=C H-bonds) are known [15][16], the examples of the N–H···N=C bonds are less numerous and involve mostly aminopyrimidines and imidazoles [13][14]. Derivatives of 3 can be of special interest as flexible supramolecular synthons [14][17] owing to

Synthesis of benzo[d]imidazo[2,1-b]benzoselenoazoles: Cs₂CO₃-mediated cyclization of 1-(2-bromoaryl)benzimidazoles with selenium

• Mio Matsumura,
• Yuki Kitamura,
• Arisa Yamauchi,
• Yoshitaka Kanazawa,
• Yuki Murata,
• Tadashi Hyodo,
• Kentaro Yamaguchi and
• Shuji Yasuike

Beilstein J. Org. Chem. 2019, 15, 2029–2035, doi:10.3762/bjoc.15.199

• could be easily prepared according to a previously reported general method [17]. The N-arylation of benzo[d]imidazoles with 1-bromo-2-fluorobenzene derivatives in the presence of K3PO4 (5 equiv) at 150 °C gave 1a–i in 45–99% yields. All synthetic details including the preparation method for 1-(2

• residue was purified by silica gel chromatography (n-hexane/AcOEt). (a) Ortep drawing of 2a (50% probability, only one of two independent molecules is shown) and (b) packing structure. The component based solvent was omitted for clarity. Cs2CO3-mediated cyclization of 1-(2-bromoaryl)imidazoles with Se

Reactions of 2-carbonyl- and 2-hydroxy(or methoxy)alkyl-substituted benzimidazoles with arenes in the superacid CF₃SO₃H. NMR and DFT studies of dicationic electrophilic species

• Dmitry S. Ryabukhin,
• Alexey N. Turdakov,
• Natalia S. Soldatova,
• Mikhail O. Kompanets,
• Alexander Yu. Ivanov,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2019, 15, 1962–1973, doi:10.3762/bjoc.15.191

• –Crafts reaction; triflic acid; Introduction Imidazoles and benzimidazoles are important heterocyclic scaffolds in pharmaceuticals and agrochemicals [1][2][3][4][5][6][7][8][9][10]. They also have applications in the fields of dyes, chemo-sensing, and fluorescent materials [3]. (Benz)imidazoles are a