Synthesis of new representatives of A₃B-type carboranylporphyrins based on meso-tetra(pentafluorophenyl)porphyrin transformations

• Victoria M. Alpatova,
• Evgeny G. Rys,
• Elena G. Kononova and
• Valentina A. Ol'shevskaya

Beilstein J. Org. Chem. 2024, 20, 767–776, doi:10.3762/bjoc.20.70

• single pentafluorophenyl ring was prepared through the regioselective nucleophilic aromatic substitution reaction of the p-fluorine atoms in 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin with 9-mercapto-m-carborane. The reaction of this porphyrin with sodium azide led to the selective substitution of

• next studied the modification of the pentafluorophenyl substituents with carborane clusters via the SNAr substitution reaction with carborane nucleophiles [17][24][25][26][27]. These reactions are well studied for porphyrin 1 [17][24][25][26][27] to afford the corresponding carborane derivatives

• fluorophenylporphyrin substituents via the boron atom. At the same time the SNAr substitution reaction for the azido-substituted porphyrin 2 with mercaptocarborane 4 also afforded the amino-substituted porphyrin 5 in 32% yield (Scheme 2). During the reaction the reduction of the azide group under the action of

Green and sustainable approaches for the Friedel–Crafts reaction between aldehydes and indoles

• Periklis X. Kolagkis,
• Eirini M. Galathri and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2024, 20, 379–426, doi:10.3762/bjoc.20.36

Facile approach to N,O,S-heteropentacycles via condensation of sterically crowded 3H-phenoxazin-3-one with ortho-substituted anilines

• Eugeny Ivakhnenko,
• Vasily Malay,
• Pavel Knyazev,
• Nikita Merezhko,
• Nadezhda Makarova,
• Oleg Demidov,
• Gennady Borodkin,
• Andrey Starikov and
• Vladimir Minkin

Beilstein J. Org. Chem. 2024, 20, 336–345, doi:10.3762/bjoc.20.34

• University, 1 Pushkin St., 355017, Stavropol, Russian Federation 10.3762/bjoc.20.34 Abstract A convenient method for the synthesis of a series of 2-(arylamino)-3H-phenoxazin-3-ones based on the nucleophilic substitution reaction between sterically crowded 3H-phenoxazin-3-one and arylamines performed by

• the crystalline samples, which is otherwise typical for solid-state reaction, was employed in this case. As seen in Scheme 2, the nucleophilic substitution reaction occured in good yield and with no restrictions in terms of amine basicity. The molecular structures of compounds 4c,d,f were determined

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

• hydride resulted in the formation of the oxepine ring by a double substitution reaction, to yield the desired dinaphthooxepine 33. The non-planar character of dinaphthooxepine bisimides was confirmed by X-ray crystal structure, and stability towards thermal or photoactivation was also established. Cyclic

Controlling the reactivity of La@C₈₂ by reduction: reaction of the La@C₈₂ anion with alkyl halide with high regioselectivity

• Yutaka Maeda,
• Saeka Akita,
• Mitsuaki Suzuki,
• Michio Yamada,
• Takeshi Akasaka,
• Kaoru Kobayashi and
• Shigeru Nagase

Beilstein J. Org. Chem. 2023, 19, 1858–1866, doi:10.3762/bjoc.19.138

• reaction is believed to occur via electron transfer, followed by the radical coupling of La@C2v-C82 and benzyl radicals, rather than by bimolecular nucleophilic substitution reaction of La@C2v-C82 anion with 1. Keywords: electron transfer; metallofullerene; radical; reduction; Introduction Fullerenes

α-(Aminomethyl)acrylates as acceptors in radical–polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping

• Angel Palillero-Cisneros,
• Paola G. Gordillo-Guerra,
• Fernando García-Alvarez,
• Olivier Jackowski,
• Franck Ferreira,
• Fabrice Chemla,
• Joel L. Terán and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2023, 19, 1443–1451, doi:10.3762/bjoc.19.103

• ZnMe2 (entries 9 and 10). This difference can be ascribed to a less favorable homolytic substitution reaction of ZnMe2 in relation to its higher analogues and is in line with previous literature observations [11]. The configuration of the major diastereomer was determined by chemical correlation (Scheme

• -promoted tandem 1,4-addition–electrophilic substitution reaction between dialkylzinc reagents and α-(aminomethyl)acrylates (N-(tert-butanesulfinyl) derivatives shown). Preparation of α-(aminomethyl)acrylates with free N–H bonds. Air-promoted 1,4-addition of Et2Zn onto α-(aminomethyl)acrylates having free N

Organic thermally activated delayed fluorescence material with strained benzoguanidine donor

• Alexander C. Brannan,
• Elvie F. P. Beaumont,
• Nguyen Le Phuoc,
• George F. S. Whitehead,
• Mikko Linnolahti and
• Alexander S. Romanov

Beilstein J. Org. Chem. 2023, 19, 1289–1298, doi:10.3762/bjoc.19.95

• containing a rigid benzoguanidine ligand in its molecular structure. Results and Discussion Synthesis and structure 4BGIPN was prepared in 70% yield by aromatic nucleophilic substitution reaction from 2,4,5,6-tetrafluoroisophthalonitrile and 5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (benzoguanidine) after

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

• individual compounds but does in fact show additional charge-transfer bands from the preassembly. After electron transfer from *PC1•− to 1d, the C(sp2)–Br bond is cleaved and the aryl radical readily reacts with B2pin2 in a radical substitution reaction yielding the borylated product 17k and a Bpin radical

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

• first reported synthesis of imipramine (3) by Schindler and Häfliger [76] proceeded by alkylation of 2a by alkyl halides. Selected N-alkylations of 1a and 2a are included in Scheme 33. N-Allylation of 1a or 2a with allyl bromide (143) can be achieved by a base-promoted substitution reaction (Scheme 33A

Nucleophile-induced ring contraction in pyrrolo[2,1-c][1,4]benzothiazines: access to pyrrolo[2,1-b][1,3]benzothiazoles

• Ekaterina A. Lystsova,
• Maksim V. Dmitriev,
• Andrey N. Maslivets and
• Ekaterina E. Khramtsova

Beilstein J. Org. Chem. 2023, 19, 646–657, doi:10.3762/bjoc.19.46

• ) [32]. The third group of approaches to the PBTA scaffold includes only one example, the intramolecular radical substitution reaction in 1-(2-bromophenyl)-5-(butylsulfanyl)pyrrolidin-2-one (Scheme 3, entry 13) [8]. The fourth group of approaches to the PBTA scaffold is the intramolecular cyclization of

• proceeds through a different pathway from the one to pyrrolobenzothiazoles 3, 7, and 12. Biologically active PBTAs. Electrophilic centers in FPDs. Approaches to PBTAs via annulation of benzothiazoles. Approaches to PBTAs via annulation of o-aminothiophenols. Approach to PBTAs via radical substitution

• reaction in 1-(2-bromophenyl)-5-(butylsulfanyl)pyrrolidin-2-one. Approach to PBTAs via intramolecular cyclizations of 1-(2-thiophenyl)pyrroles. A new approach to PBTAs via nucleophile-induced ring contraction in pyrrolo[2,1-c][1,4]benzothiazines. Reaction of APBTT 1a with methanol (2a). Derivatization of

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

• , the authors noted the reaction was stereoselective for the trans-addition product. Mechanistically, the authors proposed the reaction begins with the Cu-mediated substitution reaction of iodobenzene (66a) with KSCN to afford phenyl thiocyanate (70). The Cu complex can then undergo oxidative addition

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

• summarized so that the chemists, researchers, and pharmaceutical industries find its effectiveness in near future for the synthesis of potent, novel, and non-toxic drug molecules. Keywords: functionalization; imidazole N-oxide; mechanistic insights; multicomponent reaction; nucleophilic substitution

• reaction; Introduction Imidazole is one of the best-known heterocyclic compounds. Derivatives of imidazole are powerful molecules taking part in numerous biochemical processes and exhibiting distinctive biological activities [1][2]. The imidazole motif can be seen in several natural compounds like

A versatile way for the synthesis of monomethylamines by reduction of N-substituted carbonylimidazoles with the NaBH₄/I₂ system

• Lin Chen,
• Xuan Zhou,
• Zhiyong Chen,
• Changxu Wang,
• Shunjie Wang and
• Hanbing Teng

Beilstein J. Org. Chem. 2022, 18, 1032–1039, doi:10.3762/bjoc.18.104

• cyanoformamides [75]. However, all of these works are primarily focused on the substitution reaction of N-substituted carbonylimidazoles. In our previous work, we conveniently prepared formamides by reducing N-substituted carbonylimidazoles with NaBH4 [62] (Scheme 1). The reaction mechanism shows that the H− ion

• acted as a nucleophile to attack the carbonyl carbon to cause the imidazolium ion to leave without reducing the carbonyl group. Although this work expands the application of N-substituted carbonylimidazoles, the reaction can still be regarded as a substitution reaction, which is attributed to the weak

Molecular diversity of the base-promoted reaction of phenacylmalononitriles with dialkyl but-2-ynedioates

• Hui Zheng,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 991–998, doi:10.3762/bjoc.18.99

• , phenacylmalononitrile is also a readily available substrate, which can be easily prepared through a base-promoted substitution reaction of phenacyl bromide with malononitrile under mild conditions [11][12][13][14][15][16]. In many practical cases, phenacylmalononitriles could be conveniently generated in situ by

Synthetic strategies for the preparation of γ-phostams: 1,2-azaphospholidine 2-oxides and 1,2-azaphospholine 2-oxides

• Jiaxi Xu

Beilstein J. Org. Chem. 2022, 18, 889–915, doi:10.3762/bjoc.18.90

• )aminoalkanoic acids 86 (Scheme 15) [35][36]. This is a convenient way to synthesize γ-phosphonolactams 85. They further extended their method to synthesize cyclic O,O- and O,S-bidentate ligands with a P–N–P backbone. The substitution reaction of 3-bromopropylamine hydrogen bromide (87) and chloroethoxyphosphine

Synthesis of novel alkynyl imidazopyridinyl selenides: copper-catalyzed tandem selenation of selenium with 2-arylimidazo[1,2-a]pyridines and terminal alkynes

• Mio Matsumura,
• Kaho Tsukada,
• Kiwa Sugimoto,
• Yuki Murata and
• Shuji Yasuike

Beilstein J. Org. Chem. 2022, 18, 863–871, doi:10.3762/bjoc.18.87

• inexpensive and easy to handle Se powder as the Se source. The reaction proceeded with terminal alkynes having various substitutions, such as aryl, vinyl, and alkyl groups. The obtained alkynyl imidazopyridinyl selenide was found to undergo nucleophilic substitution reaction on Se atom using organolithium

• phenyllithium in THF at −78 °C led to a nucleophilic substitution reaction with the elimination of the ethynyl group to form the desired phenylimidazopyridinyl selenide 6a in 49% yield. In the reaction with n-butyllithium, alkyl derivative 6b was isolated in the same way. The reaction of 4aa with the Ruppert

First series of N-alkylamino peptoid homooligomers: solution phase synthesis and conformational investigation

• Maxime Pypec,
• Laurent Jouffret,
• Claude Taillefumier and
• Olivier Roy

Beilstein J. Org. Chem. 2022, 18, 845–854, doi:10.3762/bjoc.18.85

• to the Boc side chain protections. For the submonomer solution-phase synthesis of monomer 1 and oligomers 2–5, modifications from the standard synthesis conditions were required, notably for the substitution reaction. Thus, the first substitution reaction between benzyl bromoacetate and N-Boc-N

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

• aldehydes and ketones [128]. In this context, Fry and co-workers explored the electrophilic substitution reaction to synthesize 2-methyl-3-bromonaphthalene-1,4-dione (82), an important intermediate used for the synthesis of naphthoquinones functionalized with organochalcogens [127]. Compound 82 was obtained

Site-selective reactions mediated by molecular containers

• Rui Wang and
• Yang Yu

Beilstein J. Org. Chem. 2022, 18, 309–324, doi:10.3762/bjoc.18.35

• could mimic the catalysis behavior of the active sites of enzymes. In 2012, the Fujita group reported a site-selective nucleophilic substitution reaction of allylic chlorides mediated by cage host J (Figure 12) [74]. Usually, this reaction occurs both at the α and γ positions of the allylic chloride

• . Site-selective monoepoxidation of α,ω-dienes mediated by the water-soluble cavitand host E. Site-selective ring-opening reaction of epoxides mediated by cavitand I with an inwardly directed carboxylic acid module. Site-selective nucleophilic substitution reaction of allylic chlorides mediated by cage

New efficient synthesis of polysubstituted 3,4-dihydroquinazolines and 4H-3,1-benzothiazines through a Passerini/Staudinger/aza-Wittig/addition/nucleophilic substitution sequence

• Long Zhao,
• Mao-Lin Yang,
• Min Liu and
• Ming-Wu Ding

Beilstein J. Org. Chem. 2022, 18, 286–292, doi:10.3762/bjoc.18.32

• Abstract A new efficient synthesis of polysubstituted 3,4-dihydroquinazolines and 4H-3,1-benzothiazines via sequential Passerini/Staudinger/aza-Wittig/addition/nucleophilic substitution reaction has been developed. The three-component Passerini reactions of 2-azidobenzaldehydes 1, benzoic acid (2), and

1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis

• Ruan Carlos B. Ribeiro,
• Patricia G. Ferreira,
• Amanda de A. Borges,
• Luana da S. M. Forezi,
• Fernando de Carvalho da Silva and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 53–69, doi:10.3762/bjoc.18.5

• recognition of cholylglycine, which is a combination of cholic acid and glycine. The β-cyclodextrin/graphene oxide composite forms an inclusion complex with a β-NQS guest. The amino group of cholylglycine can bind to β-NQS by a nucleophilic substitution reaction, resulting in a decrease in the electrochemical

• addition to the sulfonic acid substitution reaction of position C4 of β-NQS, quinone can be involved in a redox process and, therefore, can be used as an electrode in electrochemical processes. Subsequently, Legua and co-workers [56][57] applied this method to determine amphetamines in urine. Figure 3

Synthesis of a novel aminobenzene-containing hemicucurbituril and its fluorescence spectral properties with ions

• Qingkai Zeng,
• Qiumeng Long,
• Jihong Lu,
• Li Wang,
• Yuting You,
• Xiaoting Yuan,
• Qianjun Zhang,
• Qingmei Ge,
• Hang Cong and
• Mao Liu

Beilstein J. Org. Chem. 2021, 17, 2840–2847, doi:10.3762/bjoc.17.195

• intensity. Conclusion In summary, we have presented a novel type of hemicucurbituril derivative modified with aminobenzene. Based on the fragment coupling strategy, the nitrobenzene-containing hemicucurbituril 9 was synthesized by nucleophilic substitution reaction with two fragments 7 and 8. The desired

Photophysical, photostability, and ROS generation properties of new trifluoromethylated quinoline-phenol Schiff bases

• Inaiá O. Rocha,
• Yuri G. Kappenberg,
• Wilian C. Rosa,
• Clarissa P. Frizzo,
• Nilo Zanatta,
• Marcos A. P. Martins,
• Isadora Tisoco,
• Bernardo A. Iglesias and
• Helio G. Bonacorso

Beilstein J. Org. Chem. 2021, 17, 2799–2811, doi:10.3762/bjoc.17.191

• methods, which provide active ingredients to prevent or reduce the effects of oxidative stress in cells. Recently, our research group reported the synthesis of 6-amino-4-(trifluoromethyl)quinolines, which were obtained through an electrophilic aromatic substitution reaction catalyzed by sulfuric acid from

Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds

• Alemayehu Gashaw Woldegiorgis and
• Xufeng Lin

Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185

• groups were tolerated [7]. In 2020, Tan and co-workers disclosed the phosphoric acid-catalyzed atroposelective arene functionalization of nitrosonaphthalene with indoles to form atropisomeric indole-naphthalenes 39 and indole-anilines 40 by a nucleophilic aromatic substitution reaction [61] (Scheme 13

• ). Various 2-nitrosonaphthalenes 36 and indoles 37 with different substitutions were subjected to nucleophilic aromatic substitution reaction catalyzed by CPA 11 to form an intermediate I-11, which was then re-aromatized to give I-12, and then oxidized to give 39. In addition, the intermediate I-12 was

• , this synthetic method (nucleophilic aromatic substitution reaction) is crucial for the development of alternative C–N bond-forming reactions to conventional metal-involved cross-couplings, providing axially chiral N-arylcarbazoles 60 in good yields with remarkable enantiocontrol through a

(Phenylamino)pyrimidine-1,2,3-triazole derivatives as analogs of imatinib: searching for novel compounds against chronic myeloid leukemia

• Luiz Claudio Ferreira Pimentel,
• Lucas Villas Boas Hoelz,
• Henayle Fernandes Canzian,
• Frederico Silva Castelo Branco,
• Andressa Paula de Oliveira,
• Vinicius Rangel Campos,
• Floriano Paes Silva Júnior,
• Rafael Ferreira Dantas,
• Jackson Antônio Lamounier Camargos Resende,
• Anna Claudia Cunha,
• Nubia Boechat and
• Mônica Macedo Bastos

Beilstein J. Org. Chem. 2021, 17, 2260–2269, doi:10.3762/bjoc.17.144

• )pyrimidin-2-amine (5) was obtained from the aromatic nucleophilic substitution reaction of intermediate PAPP via the formation of a diazonium salt with 84% yield, which was characterized, and its data agreed with those in the literature [29]. The carbonyl nucleophilic substitution reaction between

• obtained from the nucleophilic substitution reaction of intermediate 8 in 85% yield. The 1H and 13C NMR spectra of compounds 8 and 9 were similar, but in the IR spectrum of intermediate 9, it was possible to observe the characteristic stretching of the azide group at 2103 cm−1. The 1,3-dipolar