Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

Thiophene/selenophene-based S-shaped double helicenes: regioselective synthesis and structures

• Mengjie Wang,
• Lanping Dang,
• Wan Xu,
• Zhiying Ma,
• Liuliu Shao,
• Guangxia Wang,
• Chunli Li and
• Hua Wang

Beilstein J. Org. Chem. 2022, 18, 809–817, doi:10.3762/bjoc.18.81

• packing structures of these compounds. Spectroscopic results and our previous work showed that the combination of molecular structure change and heteroatom replacement from S to Se could precisely modulate molecular energy levels. Keywords: crystal structure; double helicene; regioselective synthesis

Regioselective synthesis of methyl 5-(N-Boc-cycloaminyl)-1,2-oxazole-4-carboxylates as new amino acid-like building blocks

• Jolita Bruzgulienė,
• Greta Račkauskienė,
• Aurimas Bieliauskas,
• Vaida Milišiūnaitė,
• Miglė Dagilienė,
• Gita Matulevičiūtė,
• Vytas Martynaitis,
• Sonata Krikštolaitytė,
• Frank A. Sløk and
• Algirdas Šačkus

Beilstein J. Org. Chem. 2022, 18, 102–109, doi:10.3762/bjoc.18.11

Efficient and regioselective synthesis of dihydroxy-substituted 2-aminocyclooctane-1-carboxylic acid and its bicyclic derivatives

• İlknur Polat,
• Selçuk Eşsiz,
• Uğur Bozkaya and
• Emine Salamci

Beilstein J. Org. Chem. 2022, 18, 77–85, doi:10.3762/bjoc.18.7

• epoxide 7, the relative free energy of 7b is higher by 10.3 kcal mol−1 than that of 7a (Figure 5). Conclusion In summary, we successfully synthesized hydroxylated cyclooctane β-amino acid 6 and its derivatives 8, 10, and 13 starting from β-lactam 2. The regioselective synthesis of lactone 8, which is a

Advances in mercury(II)-salt-mediated cyclization reactions of unsaturated bonds

• Sumana Mandal,
• Raju D. Chaudhari and
• Goutam Biswas

Beilstein J. Org. Chem. 2021, 17, 2348–2376, doi:10.3762/bjoc.17.153

• depending on the reaction conditions (Scheme 13) [53][58]. Cyclization of 4-cycloocten-1-ol (35) with Hg(OAc)2 resulted in formation of two types of fused bicyclic products, 9-oxabicyclo[3.3.1]nonane (36) and 9-oxabicyclo[4.2.1]nonane (37) (Scheme 14) [59][60]. It was observed that the regioselective

• synthesis of 9-oxabicyclo[4.2.1]nonane (37) was favored when NaBH4 and sodium acetate NaOAc were present, while in absence of NaOAc, 9-oxabicyclo[3.3.1]nonane (36) was formed as an exclusive product. In a similar manner, an aminomercuration reaction had been successfully employed in the cyclization of trans

Regioselective N-alkylation of the 1H-indazole scaffold; ring substituent and N-alkylating reagent effects on regioisomeric distribution

• Ryan M. Alam and
• John J. Keating

Beilstein J. Org. Chem. 2021, 17, 1939–1951, doi:10.3762/bjoc.17.127

• , indazole ring-closure [10][11]. For example, several reports have highlighted the use of N-alkyl or N-arylhydrazines in the regioselective synthesis of 1H-indazoles, from the corresponding ortho-haloaryl carbonyl or nitrile, in good to excellent yield (Scheme 1) [12][13][14]. Alternative strategies to

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

• materials. As such, the discovery of more effective strategies for the rapid preparation of these significant products is extremely desired. The regioselective synthesis of these compounds mainly includes (i) direct synthesis of fully decorated systems and (ii) postfunctionalization of disubstituted 1,2,3

• good antitumor activity in comparison to 5-stibanotriazoles, this reinforces the importance of synthesizing 5-stibanotriazoles [54]. A similar reaction for the regioselective synthesis of triazole disulfides 98 through a copper(I)-catalyzed cycloaddition of azides 95, alkynes 96, and tert-butyl tosyl

Microwave-assisted multicomponent reactions in heterocyclic chemistry and mechanistic aspects

• Shivani Gulati,
• Stephy Elza John and
• Nagula Shankaraiah

Beilstein J. Org. Chem. 2021, 17, 819–865, doi:10.3762/bjoc.17.71

• marketed drugs structured around indole implying its pharmacological significance such as oxypertine (27), ateviridine (28) [47] and spirooxindole-based potent cytotoxic agents 29, 30 and 31 [48]. In 2017, Lin and co-workers [49] designed a TFA-catalyzed three-component reaction for the regioselective

• synthesis of 3-functionalized indoles 34 by employing amines 32, arylglyoxal monohydrate 33 and cyclic 1,3-diketones 6 under microwave irradiation in the greener solvent system EtOH/H2O (Scheme 10). A plausible mechanism (Scheme 11) suggests a TFA-catalyzed Knoevenagel condensation between 4-hydroxy-6

Regioselective synthesis of heterocyclic N-sulfonyl amidines from heteroaromatic thioamides and sulfonyl azides

• Vladimir Ilkin,
• Vera Berseneva,
• Tetyana Beryozkina,
• Tatiana Glukhareva,
• Lidia Dianova,
• Wim Dehaen,
• Eugenia Seliverstova and
• Vasiliy Bakulev

Beilstein J. Org. Chem. 2020, 16, 2937–2947, doi:10.3762/bjoc.16.243

• amino group. Thiatriazoles are known to be unstable compounds that readily evolve nitrogen and sulfur upon heating [56]. Conclusion We have shown that the reaction of sulfonyl azides with thioamides can serve as the basis for a general and efficient method for the regioselective synthesis of N-sulfonyl

Highly selective Diels–Alder and Heck arylation reactions in a divergent synthesis of isoindolo- and pyrrolo-fused polycyclic indoles from 2-formylpyrrole

• Carlos H. Escalante,
• Eder I. Martínez-Mora,
• Carlos Espinoza-Hicks,
• Alejandro A. Camacho-Dávila,
• Fernando R. Ramos-Morales,
• Francisco Delgado and
• Joaquín Tamariz

Beilstein J. Org. Chem. 2020, 16, 1320–1334, doi:10.3762/bjoc.16.113

• [3,4-e]indoles, which served as precursors in the regioselective synthesis of aza-polycyclic skeletons via an intramolecular Heck arylation reaction. Through the latter reaction, the 3-(N-benzyl-2-pyrrolyl)acrylates give rise to 3-(pyrrolo[2,1-a]isoindol-3-yl)acrylates. A further oxidative

A systematic review on silica-, carbon-, and magnetic materials-supported copper species as efficient heterogeneous nanocatalysts in “click” reactions

• Pezhman Shiri and
• Jasem Aboonajmi

Beilstein J. Org. Chem. 2020, 16, 551–586, doi:10.3762/bjoc.16.52

Regio- and stereoselective synthesis of new ensembles of diversely functionalized 1,3-thiaselenol-2-ylmethyl selenides by a double rearrangement reaction

• Svetlana V. Amosova,
• Andrey A. Filippov,
• Nataliya A. Makhaeva,
• Alexander I. Albanov and
• Vladimir A. Potapov

Beilstein J. Org. Chem. 2020, 16, 515–523, doi:10.3762/bjoc.16.47

• rearrangements occurred by a nucleophilic attack of the selenocyanate anion at two different carbon atoms of the seleniranium intermediate. The efficient regioselective synthesis of alkyl, allyl, 2-propynyl, benzyl, 4-fluorobenzyl, and 2-pyridinylmethyl 1,3-thiaselenol-2-ylmethyl selenides was developed based on

• , regioselective synthesis of hitherto unknown organyl 1,3-thiaselenol-2-ylmethyl selenides 6a–l in high yields (Scheme 8). The synthesis was based on the generation of sodium 1,3-thiaselenol-2-ylmethylselenolate by the reaction of NaBH4 with compound 4 in methanol followed by nucleophilic substitution reactions

Synthesis of 3-alkenylindoles through regioselective C–H alkenylation of indoles by a ruthenium nanocatalyst

• Abhijit Paul,
• Debnath Chatterjee,
• Srirupa Banerjee and
• Somnath Yadav

Beilstein J. Org. Chem. 2020, 16, 140–148, doi:10.3762/bjoc.16.16

• reaction of aza compounds [43][44]. Again, a Ru nanoparticle-catalysed C–H selenylation of indoles was reported by Lin et al. [45]. Herein, we report the Ru-catalysed regioselective synthesis of C3 alkenylindoles using a near-naked, surfactant-free, and recyclable Ru nanocatalyst in a heterogeneous manner

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

• not formed. Atmospheric oxygen has oxidized Cu(I) to Cu(II). This Cu(II) acts as an initiator for a single electron transfer (SET) process, to proceed the reaction with benzylamine. A regioselective synthesis of imidazo[1,2-a]pyridines was reported by the group of Kamal and Reddy [123]. They have

Enhanced single-isomer separation and pseudoenantiomer resolution of new primary rim heterobifunctionalized α-cyclodextrin derivatives

• Iveta Tichá,
• Gábor Benkovics,
• Milo Malanga and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2018, 14, 2829–2837, doi:10.3762/bjoc.14.261

• . investigated the regioselective synthesis of tris(4-tert-butylphenyl)methyl ethers on the primary rim of α-CD which resulted in predominant AD species [20]. Trityl groups for regioselective bi- and trifunctionalization of α-CD were also investigated [21]. Thus, the use of either a direct single-step or

5-Aminopyrazole as precursor in design and synthesis of fused pyrazoloazines

• Ranjana Aggarwal and
• Suresh Kumar

Beilstein J. Org. Chem. 2018, 14, 203–242, doi:10.3762/bjoc.14.15

• conditions makes it a sought after the procedure for the synthesis of pyrazolo[1,5-a]pyrimidines. In another report, Aggarwal et al. [90] have described a regioselective synthesis of 2-H/methyl-3-phenyl-7-trifluoromethylpyrazolo[1,5-a]pyrimidines 124 by condensing 4-aryl-5-aminopyrazoles 123 with an

• -aminopyrazole derivatives 16/126 with β,γ-unsaturated-γ-alkoxy-α-ketoesters 175 for the regioselective synthesis of pyrazolo[1,5-a]pyrimidines 177 in refluxing ethanol. The reaction provided high regioselectivity compared to other 1,3-dielectrophiles like 1,3-dicarbonyl compounds. The reaction was proposed to

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

Regioselective decarboxylative addition of malonic acid and its mono(thio)esters to 4-trifluoromethylpyrimidin-2(1H)-ones

• Sergii V. Melnykov,
• Andrii S. Pataman,
• Yurii V. Dmytriv,
• Svitlana V. Shishkina,
• Mykhailo V. Vovk and
• Volodymyr A. Sukach

Beilstein J. Org. Chem. 2017, 13, 2617–2625, doi:10.3762/bjoc.13.259

• . Consequently, the nucleophilic attack on the C=N double bond becomes equally probable thus leading to the loss of regioselectivity. Fortunately, allyl and various benzyl or phenyl substituents in derivatives 2f–m allowed the regioselective synthesis of products 6f–m in high yields (Table 4, entries 5–12). We

Synthesis and supramolecular properties of regioisomers of mononaphthylallyl derivatives of γ-cyclodextrin

• Markéta Bláhová,
• Sergey K. Filippov,
• Lubomír Kováčik,
• Jiří Horský,
• Simona Hybelbauerová,
• Zdenka Syrová,
• Tomáš Křížek and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2017, 13, 2509–2520, doi:10.3762/bjoc.13.248

• -substituted ones. To separate pure regioisomers from their mixture is tricky. Their direct regioselective synthesis is possible, although not easy, because hydroxy groups at different positions of CD have different properties; the hydroxy group at position 6 is the most nucleophilic and basic one, the hydroxy

Synthesis, effect of substituents on the regiochemistry and equilibrium studies of tetrazolo[1,5-a]pyrimidine/2-azidopyrimidines

• Elisandra Scapin,
• Paulo R. S. Salbego,
• Caroline R. Bender,
• Alexandre R. Meyer,
• Anderson B. Pagliari,
• Tainára Orlando,
• Geórgia C. Zimmer,
• Clarissa P. Frizzo,
• Helio G. Bonacorso,
• Nilo Zanatta and
• Marcos A. P. Martins

Beilstein J. Org. Chem. 2017, 13, 2396–2407, doi:10.3762/bjoc.13.237

• efficient and regioselective synthesis of pyrazolo[1,5-a]pyrimidines and aryl[heteroaryl]pyrazolo[1,5-a]pyrimidines in acetic acid under reflux. The regioselectivity was attributed to the high nucleophilicity of the amino group in 3-amino-5-methyl-1H-pyrazole and the high electrophilicity of the β-carbon

• showed that the structure of the R group affects the regiochemistry of the products formed. The β-enaminones 1a–g (R = aryl) result predominantly in 5-aryl-substituted tetrazolo[1,5-a]pyrimidines 3a–g. β-Enaminones 1h,i (R = CF3 and CCl3) result in a highly regioselective synthesis of tetrazolo[1,5-a

• , our research group demonstrated a highly regioselective synthesis of a series of trifluoromethylated tetrazolo[1,5-a]pyrimidines with potent antimicrobial activity [37]. The reaction between several β-alkoxyvinyl trifluoromethyl ketones [CF3C(O)CH=C(R)OCH3] (in which R = Ph, 4-F–C6H4, 4-Cl–C6H4, 4-Br

p-tert-Butylthiacalix[4]arenes functionalized by N-(4’-nitrophenyl)acetamide and N,N-diethylacetamide fragments: synthesis and binding of anionic guests

• Alena A. Vavilova and
• Ivan I. Stoikov

Beilstein J. Org. Chem. 2017, 13, 1940–1949, doi:10.3762/bjoc.13.188

• thiacalix[4]arene variously substituted at the lower rim form 1,2-, 1,3-di- and trisubstituted macrocycles [42], depending on the nature of the alkali metal carbonates and solvent. In this paper, we describe the regioselective synthesis of p-tert-butylthiacalix[4]arene monosubstituted at the lower rim by N

• containing N-(4’-nitrophenyl)acetamide and N,N-diethylacetamide moieties at the lower rim The regioselective synthesis of p-tert-butylthiacalix[4]arenes partially substituted at the lower rim, is an important challenge because it allows the sequential functionalization of the macrocyclic platform with the

Switchable highly regioselective synthesis of 3,4-dihydroquinoxalin-2(1H)ones from o-phenylenediamines and aroylpyruvates

• Juraj Dobiaš,
• Marek Ondruš,
• Gabriela Addová and
• Andrej Boháč

Beilstein J. Org. Chem. 2017, 13, 1350–1360, doi:10.3762/bjoc.13.132

• characterised as regioisomeric mixtures [22]. Nevertheless, most of the nonsymmetrical 3,4-dihydroquinoxalin-2(1H)-ones are required in their pure form (Figure 1). To the best of our knowledge, there is only one paper which deals with the regioselective synthesis of 3-acylmethylidene-3,4-dihydroquinoxalin-2(1H

• ) (natively preferring SYN regioselectivity, see Table 1, entry 4, column 3) complicated the desired reaction. The other possibility was to perform the regioselective synthesis of 17d (ANTI) from an appropriate furan-2,3-dione 13 (Scheme 2). The preparation of 13 failed in our hands. Therefore, we decided to

• or the contrary regioselectivity of activated species 12c,d (prepared in situ from appropriate 12 by DMAP – 12c or HOBt/DIC additives – 12d) (Scheme 6). Conclusion Simple reaction conditions were discovered for predictable and switchable highly regioselective synthesis of 3,4-dihydroquinoxaline-2(1H

Orthogonal protection of saccharide polyols through solvent-free one-pot sequences based on regioselective silylations

• Serena Traboni,
• Emiliano Bedini and
• Alfonso Iadonisi

Beilstein J. Org. Chem. 2016, 12, 2748–2756, doi:10.3762/bjoc.12.271

• amount of TBAB, pyridine and TBDMSCl, the regioselective synthesis of di-O-TBDMS derivatives was achieved at 50 °C in satisfying yields from glycosides 1 and 3 (Table 3, entries 1 and 2), and glycal 8 (entry 3). Double silylation at primary positions of the disaccharide lactoside 20 [60] also proved

Combined experimental and theoretical studies of regio- and stereoselectivity in reactions of β-isoxazolyl- and β-imidazolyl enamines with nitrile oxides

• Ilya V. Efimov,
• Marsel Z. Shafikov,
• Nikolai A. Beliaev,
• Natalia N. Volkova,
• Tetyana V. Beryozkina,
• Wim Dehaen,
• Zhijin Fan,
• Viktoria V. Grishko,
• Gert Lubec,
• Pavel A. Slepukhin and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2016, 12, 2390–2401, doi:10.3762/bjoc.12.233

• contrast to our approach, these methods are not applicable for the regioselective synthesis of compounds containing a 3-aryl-4-carboxyisoxazole fragment, a structural motif in the anticancer pyrazolylisoxazole, and rather the 3,5-disubstituted isoxazole (compound 5, Scheme 2) is expected [12]. The presence

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162