A novel three-component reaction between isocyanides, alcohols or thiols and elemental sulfur: a mild, catalyst-free approach towards O-thiocarbamates and dithiocarbamates

• András György Németh,
• György Miklós Keserű and
• Péter Ábrányi-Balogh

Beilstein J. Org. Chem. 2019, 15, 1523–1533, doi:10.3762/bjoc.15.155

• as enzyme inhibitors [26] or antitumor agents [27]. These species are also used as valuable synthetic intermediates [28] and chemosensors for mercury and silver [29][30]. The general methods for the synthesis of O-thiocarbamates and dithiocarbamates traditionally rely on substitution reactions of the

Coordination chemistry and photoswitching of dinuclear macrocyclic cadmium-, nickel-, and zinc complexes containing azobenzene carboxylato co-ligands

• Jennifer Klose,
• Tobias Severin,
• Peter Hahn,
• Alexander Jeremies,
• Jens Bergmann,
• Daniel Fuhrmann,
• Jan Griebel,
• Bernd Abel and
• Berthold Kersting

Beilstein J. Org. Chem. 2019, 15, 840–851, doi:10.3762/bjoc.15.81

• cadmium complexes 1, 6 and 8, on the other hand, were prepared by substitution reactions involving the known chlorido-bridged [Ni2L(μ-Cl)]+ or [Cd2L(μ-Cl)]+ precursors and the respective azobenzene carboxylates. All complexes were isolated as ClO4− salts with yields between 76% and 91%. The perchlorate

Synthesis and fluorescent properties of N(9)-alkylated 2-amino-6-triazolylpurines and 7-deazapurines

• Andrejs Šišuļins,
• Jonas Bucevičius,
• Yu-Ting Tseng,
• Irina Novosjolova,
• Kaspars Traskovskis,
• Ērika Bizdēna,
• Huan-Tsung Chang,
• Sigitas Tumkevičius and
• Māris Turks

Beilstein J. Org. Chem. 2019, 15, 474–489, doi:10.3762/bjoc.15.41

• -triazolylpurine and 7-deazapurine derivatives is described. A new C(2)-regioselectivity in the nucleophilic aromatic substitution reactions of 9-alkylated-2,6-diazidopurines and 7-deazapurines with secondary amines has been disclosed. The obtained intermediates, 9-alkylated-2-amino-6-azido-(7-deaza)purines, were

• derivatives as key starting materials. We have reported here for the first time that 9-alkyl-2,6-diazidopurines exhibit C(2)-selectivity in nucleophilic aromatic substitution reactions with amines. A similar selectivity was observed also for 9-alkyl-2,6-diazido-7-deazapurines. We have also demonstrated that

Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

• Stanislav V. Lozovskiy,
• Alexander Yu. Ivanov,
• Olesya V. Khoroshilova and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2018, 14, 2897–2906, doi:10.3762/bjoc.14.268

• cases, these reactions were unselective. For instance, for allene 2a, mixtures of butadiene Z-3a and alcohol Z-4a were obtained. To overcome this obstacle we decided to use 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP), which was known to form the corresponding ether for further substitution reactions [33

An amine protecting group deprotectable under nearly neutral oxidative conditions

• Shahien Shahsavari,
• Chase McNamara,
• Mark Sylvester,
• Emily Bromley,
• Savannah Joslin,
• Bao-Yuan Lu and
• Shiyue Fang

Beilstein J. Org. Chem. 2018, 14, 1750–1757, doi:10.3762/bjoc.14.149

• , the dM-Dmoc group is expected to be more stable under nucleophilic conditions, which will allow many transformations including base hydrolysis of esters and amides, hydride reduction of carbonyl compounds, and a wide range of nucleophilic substitution reactions to be carried out without losing the

Rapid transformation of sulfinate salts into sulfonates promoted by a hypervalent iodine(III) reagent

• Elsa Deruer,
• Vincent Hamel,
• Samuel Blais and
• Sylvain Canesi

Beilstein J. Org. Chem. 2018, 14, 1203–1207, doi:10.3762/bjoc.14.101

• , decarboxylation, and fragmentation [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27]. The sulfonate group is a useful functionality frequently employed as a leaving group in substitution reactions. Production of sulfonates [28] from alcohols generally involves reaction with a

Synthesis and stability of strongly acidic benzamide derivatives

• Frederik Diness,
• Niels J. Bjerrum and
• Mikael Begtrup

Beilstein J. Org. Chem. 2018, 14, 523–530, doi:10.3762/bjoc.14.38

• trifluoromethanesulfonamide group are reported. Novel derivatives of these types of acids were synthesized in good yields. The generated N-triflylbenzamides were further functionalized through cross-coupling and nucleophilic aromatic substitution reactions. All compounds were stable in dilute aqueous solutions. Studies of

• ) or trifluoroacetic acid (3) are not readily modified, and changing substituents on these acids will heavily impact their pKa value (Figure 1). In contrast, halogenated benzoic acid derivatives are easily functionalized through cross-coupling [4][5] or nucleophilic aromatic substitution reactions

• Strategic Research Foundation of Energy and Environment is acknowledged for supporting this research (Grant 2104-05-0026). Lundbeck A/S is acknowledged for supporting research within nucleophilic aromatic substitution reactions.

Stereochemical outcomes of C–F activation reactions of benzyl fluoride

• Neil S. Keddie,
• Pier Alexandre Champagne,
• Justine Desroches,
• Jean-François Paquin and
• David O'Hagan

Beilstein J. Org. Chem. 2018, 14, 106–113, doi:10.3762/bjoc.14.6

• years, there has been an increasing interest in C–F bond activation [2], with a view to using organic bound fluoride as a leaving group in substitution reactions that typically require more activated leaving groups. Such an approach could circumvent the requirement for protecting groups in multistep

• explore the stereointegrity of the aforementioned reactions using enantiopure 7-[2H1]-(R)-benzyl fluoride ((R)-1, Figure 2) as a primary, yet chiral electrophile [10]. Substitution reactions of benzyl fluoride (1) will generate substituted products that retain the deuterium atom, and the degree of

• reactions using a mixture of nucleophiles (for direct substitutions) and aryls (for Friedel–Crafts reactions) to give products 5–9. The nucleophilic substitution reactions of 1 are shown in Table 1 and Table 2, and were all conducted using either a mixture of water/isopropanol, or tris(hydroxymethyl)propane

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• –S bonds were developed and already excellently reviewed, including nucleophilic substitution reactions between S-nucleophiles and organic electrophiles, metal-catalyzed C–S bond formations and organocatalytic or enzymatic approaches [15][16][18][20][21][22]. This review provides a brief overview

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

Binding abilities of polyaminocyclodextrins: polarimetric investigations and biological assays

• Marco Russo,
• Daniele La Corte,
• Annalisa Pisciotta,
• Serena Riela,
• Rosa Alduina and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2017, 13, 2751–2763, doi:10.3762/bjoc.13.271

• a different number of polyamine branches linked to the CD scaffold, that are isolated as partial hydrohalides. In fact, the same polyamine unit can undergo multiple substitution reactions (a possible mechanistic scheme is depicted in Supporting Information File 1, Figure S1), on the same N atom or

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

• Satoru Mori and
• Norio Shibata

Beilstein J. Org. Chem. 2017, 13, 2273–2296, doi:10.3762/bjoc.13.224

• conditions (Scheme 10) [129]. There are two methods to synthesize subphthalocyanine derivatives, mainly peripheral functionalization and substitution of axial positions. Among them, substitution reactions at the axial position can easily deliver many subphthalocyanine derivatives by coordinating various

• chemical species with one subphthalocyanine as a foothold. However, it is known that axial substitution reactions proceed with low yield with ordinary subphthalocyanine [130]. On the other hand, TFEO-subPc remarkably improves the substitution activity at its axial position, and the axial substitution

The effect of milling frequency on a mechanochemical organic reaction monitored by in situ Raman spectroscopy

• Patrick A. Julien,
• Ivani Malvestiti and
• Tomislav Friščić

Beilstein J. Org. Chem. 2017, 13, 2160–2168, doi:10.3762/bjoc.13.216

• situ XRPD monitoring of the formation of glycinium oxalate salts from γ-glycine and oxalic acid dihydrate [42]. Other examples of explorations of the effect of milling frequency on mechanochemical reactivity include aromatic substitution reactions [43] and the synthesis of nitrogen-doped titania [44

Preparation of imidazo[1,2-a]-N-heterocyclic derivatives with gem-difluorinated side chains

• Layal Hariss,
• Kamal Bou Hadir,
• Mirvat El-Masri,
• Thierry Roisnel,
• René Grée and
• Ali Hachem

Beilstein J. Org. Chem. 2017, 13, 2115–2121, doi:10.3762/bjoc.13.208

• , respectively. On the other hand, two nucleophilic substitution reactions using phenol and morpholine gave the expected heterocycles 10 and 11 in 73% and 23% yields, respectively. Conclusion In summary, we developed a short and completely regioselective method for the synthesis of imidazo[1,2-a]-N-heterocycles

• . Coupling and substitution reactions. Supporting Information Supporting Information File 310: Experimental details and characterization data of new compounds with copies of 1H, 13C and 19F NMR spectra. Acknowledgements This work was financially supported by the Research Grant Program at Lebanese

Main group mechanochemistry

• Agota A. Gečiauskaitė and
• Felipe García

Beilstein J. Org. Chem. 2017, 13, 2068–2077, doi:10.3762/bjoc.13.204

• ) (Cp′ = C5Me4(n-Pr)). Mechanochemical synthesis of the Ar-BIAN ligands and indium(III) complexes (top). One-pot synthesis of an indium complex (bottom). Synthesis of germanes from germanium (Ge) or germanium oxide (GeO2). Ball-milling nucleophilic substitution reactions to produce acyclic and cyclic

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• Coville and co-workers presented solvent-free organometallic transformations (e.g., migratory insertion and ligand substitution reactions) at elevated temperature (Scheme 44) which have close resemblance to mechanochemistry [173]. The examples of mechanochemical organometallic complex synthesis are

Influence of the milling parameters on the nucleophilic substitution reaction of activated β-cyclodextrins

• László Jicsinszky,
• Kata Tuza,
• Giancarlo Cravotto,
• Andrea Porcheddu,
• Francesco Delogu and
• Evelina Colacino

Beilstein J. Org. Chem. 2017, 13, 1893–1899, doi:10.3762/bjoc.13.184

• . The reaction was performed in a planetary ball mill and the processing parameters were systematically varied with the aim of pointing out their influence on the nucleophilic substitution reactions in terms of rate and yield. Specifically systematic variation involved rotation speed, milling tool

α-Acetoxyarone synthesis via iodine-catalyzed and tert-butyl hydroperoxide-mediateded self-intermolecular oxidative coupling of aryl ketones

• Liquan Tan,
• Cui Chen and
• Weibing Liu

Beilstein J. Org. Chem. 2017, 13, 1079–1084, doi:10.3762/bjoc.13.107

• products and pharmaceuticals, and α-acetoxyaryl ketones are widely used as synthetic intermediates [1][2][3][4][5]. Traditional methods for the preparation of α-acyloxy ketones focus on the substitution reactions of α-halo carbonyl compounds with alkaline carboxylates or carboxylic acids [6][7], and

Metal-free hydroarylation of the side chain carbon–carbon double bond of 5-(2-arylethenyl)-3-aryl-1,2,4-oxadiazoles in triflic acid

• Anna S. Zalivatskaya,
• Dmitry S. Ryabukhin,
• Marina V. Tarasenko,
• Alexander Yu. Ivanov,
• Irina A. Boyarskaya,
• Elena V. Grinenko,
• Ludmila V. Osetrova,
• Eugeniy R. Kofanov and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2017, 13, 883–894, doi:10.3762/bjoc.13.89

• xylenes, mesitylene, pseudocumene, or durene gave mixtures of oligomeric products. Probably, these products are formed through multiple electrophilic substitution reactions of these arenes by the reactive dication species D. When oxadiazole 1b reacted with tert-butylbenzene (Table 2, entry 10), product 2f

Fluorinated cyclohexanes: Synthesis of amine building blocks of the all-cis 2,3,5,6-tetrafluorocyclohexylamine motif

• Tetiana Bykova,
• Nawaf Al-Maharik,
• Alexandra M. Z. Slawin and
• David O'Hagan

Beilstein J. Org. Chem. 2017, 13, 728–733, doi:10.3762/bjoc.13.72

• motif by the wider research community requires that a range of building blocks be prepared. It has proven relatively straightforward to prepare the phenyl derivative 2 and then subsequent elaboration to a range of functionalized analogues by standard electrophilic aromatic substitution reactions (Figure

Nucleophilic displacement reactions of 5′-derivatised nucleosides in a vibration ball mill

• Olga Eguaogie,
• Patrick F. Conlon,
• Francesco Ravalico,
• Jamie S. T. Sweet,
• Thomas B. Elder,
• Louis P. Conway,
• Marc E. Lennon,
• David R. W. Hodgson and
• Joseph S. Vyle

Beilstein J. Org. Chem. 2017, 13, 87–92, doi:10.3762/bjoc.13.11

• liquid [13][14][15]. Recently, Jicsinszky et al. described using a planetary ball mill to perform substitution reactions of 6I-O-(p-toluenesulfonyl)-β-cyclodextrin (Ts-β-CD) with azide, halide or thiolate nucleophiles and thereby avoided intramolecular cyclisation (commonly found under solution-phase

Experimental and theoretical investigations into the stability of cyclic aminals

• Edgar Sawatzky,
• Antonios Drakopoulos,
• Martin Rölz,
• Christoph Sotriffer,
• Bernd Engels and
• Michael Decker

Beilstein J. Org. Chem. 2016, 12, 2280–2292, doi:10.3762/bjoc.12.221

• the strong non-nucleophilic base t-BuOK to give compound 12a. The target compound 13a could then be obtained by reduction of 12 with LiAlH4. As the substitution reactions using 11 failed with iPrI, a second synthetic pathway was pursued to alter the substituents at the N-1 nitrogen atom of the

Synthesis of 2-oxindoles via 'transition-metal-free' intramolecular dehydrogenative coupling (IDC) of sp² C–H and sp³ C–H bonds

• Nivesh Kumar,
• Santanu Ghosh,
• Subhajit Bhunia and
• Alakesh Bisai

Beilstein J. Org. Chem. 2016, 12, 1153–1169, doi:10.3762/bjoc.12.111

• -iodination at room temperature, where substitution reactions would be unlikely, considering the fact that the substitution has to occur at the sterically congested tertiary iodide 24. However, to our surprise, when C-iodination of 5a was carried out at rt, we found that it also afforded 2-oxindole 4a in 30

Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

• Barry M. Trost,
• Michael C. Ryan and
• Meera Rao

Beilstein J. Org. Chem. 2016, 12, 1136–1152, doi:10.3762/bjoc.12.110

• substitution reactions [42] (Figure 1b), would be able to impart sufficiently useful enantioselectivities on these complex, drug-like molecules. While the idea certainly was appealing at first glance, this reaction is complicated by the fact that the 1,6- and 1,7-enyne substrates contain a stereogenic center

1H-Imidazol-4(5H)-ones and thiazol-4(5H)-ones as emerging pronucleophiles in asymmetric catalysis

• Antonia Mielgo and
• Claudio Palomo

Beilstein J. Org. Chem. 2016, 12, 918–936, doi:10.3762/bjoc.12.90

• bearing the quinoyl moiety provided once again better stereochemical results than 2-naphthylthiazolones. 2.2.3 Iridium-catalyzed allylic substitution reactions. Allylic substitution reactions catalyzed by cyclometalated iridium phosphoramidite complexes constitute a powerful tool for the construction of C

• of thiazol-4(5H)-ones as pronucleophiles in asymmetric catalytic reactions has been investigated in the Michael addition reaction to nitroalkenes and α-silyloxyenones, phosphine-catalyzed γ-addition to allenoates and alkynoates, α-amination reactions and iridium-catalyzed allylic substitution

• reactions. 2.2.1 Michael addition reactions, nitroalkenes as acceptors. The first example of the utility of the thiazol-4(5H)-ones 2 as pronucleophiles in asymmetric catalysis was reported in 2013 in the Michael addition to nitroalkenes catalyzed by the bifunctional ureidopeptide-like Brønsted base C5