The selective electrochemical fluorination of S-alkyl benzothioate and its derivatives

• Shunsuke Kuribayashi,
• Tomoyuki Kurioka,
• Shinsuke Inagi,
• Ho-Jung Lu,
• Biing-Jiun Uang and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2018, 14, 389–396, doi:10.3762/bjoc.14.27

• strongly electron-withdrawing benzoyl group attached to the sulfur atom. Benzyl thiocyanate is also known to be oxidized at a high potential which is similar to that of 1a [21]. Anodic fluorination of S-butyl benzothioates Next, we carried out the anodic fluorination of 1a as a model compound under various

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

• with white light then triggers a light-induced electron transfer from the anion to the aryl halide, releasing the halide as an anion and resulting in a thiyl radical and an aryl radical. Finally, radical–radical cross-coupling yields the respective diaryl sulfide. Ammonium thiocyanate Formation of

• thiocyanates The first photoredox-catalyzed thiocyanation reaction using ammonium thiocyanate as starting material was published in 2014 by Li and co-workers (Scheme 25) [60]. They envisioned that photooxidation of ammonium thiocyanate would lead to a reactive thiocyanate radical. Subsequent radical addition

• reaction for gram-scale synthesis with a remarkably low catalyst loading of 0.1 mol %. Oxygen plays an important role in the proposed mechanism: it regenerates the catalyst by aerobic oxidation and oxidizes the carbon-centred radical intermediate, obtained by radical addition of a thiocyanate radical to

Dialkyl dicyanofumarates and dicyanomaleates as versatile building blocks for synthetic organic chemistry and mechanistic studies

• Grzegorz Mlostoń and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2017, 13, 2235–2251, doi:10.3762/bjoc.13.221

• presence of Al2O3·KF in acetonitrile at room temperature (rt) [9]. Another efficient method for the preparation of dialkyl esters E-1 relies on the usage of alkyl bromo(cyano)acetates 3, which upon treatment with potassium thiocyanate in aqueous acetonitrile at room temperature are converted into the

Mechanochemical synthesis of thioureas, ureas and guanidines

• Vjekoslav Štrukil

Beilstein J. Org. Chem. 2017, 13, 1828–1849, doi:10.3762/bjoc.13.178

• route to primary monosubstituted thioureas 32 [42]. Primary thioureas are typically prepared in solution from benzoyl chloride and ammonium thiocyanate or by condensation of amine hydrochlorides and potassium thiocyanate [43][44]. Our strategy was to synthesize the desired thiocarbamoyl benzotriazole in

Phosphorus pentasulfide mediated conversion of organic thiocyanates to thiols

• Chandra Kant Maurya,
• Avik Mazumder and
• Pradeep Kumar Gupta

Beilstein J. Org. Chem. 2017, 13, 1184–1188, doi:10.3762/bjoc.13.117

• required by reported methods, and provides an attractive alternative to the existing methods for the conversion of organic thiocyanates to thiols. Keywords: dithiocarbamate; phosphorus pentasulfide; thiocyanate; thiol; toluene; Introduction Thiols constitute an important group of sulfur-containing

• conversion of thiocyanates to the corresponding thiols. Results and Discussion Initially, for reaction condition optimizations, benzyl thiocyanate was chosen as model substrate and was reacted with P2S5 in different organic solvents (Table 1). Although, the reaction proceeded in solvents including benzene

• order to further study the scope and limitations of the method, different thiocyanates were treated with P2S5 in refluxing toluene to get the corresponding thiols in good to moderate yield in short reaction time (Table 2). The thiocyanate substrates were prepared by the reaction of alkyl halide with

Extrusion – back to the future: Using an established technique to reform automated chemical synthesis

• Deborah E. Crawford

Beilstein J. Org. Chem. 2017, 13, 65–75, doi:10.3762/bjoc.13.9

• well as the reaction between triphenylphosphine and nickel thiocyanate, both in the presence of stoichiometric amounts of MeOH (Figure 6) [2]. High-quality products were obtained, as determined by 1H NMR spectroscopy, PXRD analysis (which gave sharp diffraction patterns, indicating high crystallinity

From steroids to aqueous supramolecular chemistry: an autobiographical career review

• Bruce C. Gibb

Beilstein J. Org. Chem. 2016, 12, 684–701, doi:10.3762/bjoc.12.69

• will decrease the solubility of a protein causing it to precipitate from solution. In contrast, salts such as sodium thiocyanate cause proteins to become more soluble, and in doing so break apart their tertiary structure. For a long time it has been appreciated that it is the anion that plays the more

Enabling technologies and green processes in cyclodextrin chemistry

• Giancarlo Cravotto,
• Marina Caporaso,
• Laszlo Jicsinszky and
• Katia Martina

Beilstein J. Org. Chem. 2016, 12, 278–294, doi:10.3762/bjoc.12.30

• . Monosubstituted CD derivative preparation Mono 6I-(p-toluenesulfonyl)-β-CD is the most popular of the CD derivatives because it is a key intermediate in the synthesis of important amino, azido, thio, thiocyanate and halo-derivatives. 6I-(p-toluenesulfonyl)-β-CD was efficiently prepared in an US-assisted procedure

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene: the effect of planarisation on charge transport properties

• Rupert G. D. Taylor,
• Joseph Cameron,
• Iain A. Wright,
• Neil Thomson,
• Olena Avramchenko,
• Alexander L. Kanibolotsky,
• Anto R. Inigo,
• Tell Tuttle and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1148–1154, doi:10.3762/bjoc.11.129

• Compounds 5 [15] and 6 [16] were prepared according to the relevant literature. Compound 4 was prepared in three steps starting with 1-bromooctan-2-one (Scheme 1). The substitution of the bromine atom for a thiocyanate group gave 1-thiocyanatooctan-2-one, which was subsequently cyclised under acidic

Advances in the synthesis of functionalised pyrrolotetrathiafulvalenes

• Luke J. O’Driscoll,
• Sissel S. Andersen,
• Marta V. Solano,
• Dan Bendixen,
• Morten Jensen,
• Troels Duedal,
• Jess Lycoops,
• Cornelia van der Pol,
• Rebecca E. Sørensen,
• Karina R. Larsen,
• Kenneth Myntman,
• Christian Henriksen,
• Stinne W. Hansen and
• Jan O. Jeppesen

Beilstein J. Org. Chem. 2015, 11, 1112–1122, doi:10.3762/bjoc.11.125

• . The reduction of the thiocyanate moieties with LiAlH4 afforded the air-sensitive intermediate 18 (not characterised), which was treated with 1,1’-carbonyldiimidazole to afford 7, in 83% yield over the two steps. Preparation of functionalised MPTTFs and BPTTFs Coupling reactions Pyrrole-annelated TTF

Synthesis of nanodiamond derivatives carrying amino functions and quantification by a modified Kaiser test

• Gerald Jarre,
• Steffen Heyer,
• Elisabeth Memmel,
• Thomas Meinhardt and
• Anke Krueger

Beilstein J. Org. Chem. 2014, 10, 2729–2737, doi:10.3762/bjoc.10.288

• . This system has been successfully used for the functionalization of fullerenes [15]. The precursor 8 was synthesized according to Martinez et al. starting from cyclobutanone and methyl thiocyanate [16]. The cyclobutene ring opens at temperatures around 190 °C and the ortho-quinodimethane is formed in

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

• and purification on silica gel finally afforded the β-alkynyl-enolphosphate in 61–75% yield [58]. Azide, nitrile and thiocyanate were three other nucleophilic species used to produce pseudohalogenated phosphorus species by the AT reaction. Among them, the commercially available diphenyl

Use of 3-[¹⁸F]fluoropropanesulfonyl chloride as a prosthetic agent for the radiolabelling of amines: Investigation of precursor molecules, labelling conditions and enzymatic stability of the corresponding sulfonamides

• Reik Löser,
• Steffen Fischer,
• Achim Hiller,
• Martin Köckerling,
• Uta Funke,
• Aurélie Maisonial,
• Peter Brust and
• Jörg Steinbach

Beilstein J. Org. Chem. 2013, 9, 1002–1011, doi:10.3762/bjoc.9.115

• Chemistry Group, Albert-Einstein-Straße 3a, 18059 Rostock, Germany 10.3762/bjoc.9.115 Abstract 3-[18F]Fluoropropanesulfonyl chloride, a recently proposed prosthetic agent for fluorine-18 labelling, was prepared in a two-step radiosynthesis via 3-[18F]fluoropropyl thiocyanate as an intermediate. Two

• of 3-[18F]fluoropropyl thiocyanate to the corresponding sulfonyl chloride with the potential for automation have been identified. The reaction of 3-[18F]fluoropropanesulfonyl chloride with eight different aliphatic and aromatic amines was investigated and the identity of the resulting 18F-labelled

• are easily accessible, sufficiently stable to oxidation, and nonhygroscopic. Li et al. [18] decided to use a propyl spacer between the fluorine-18 atom and the thiocyanate moiety as radiofluorination by nucleophilic substitution proceeds easier at aliphatic than at aromatic electrophilic centres. In

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

Nano copper oxide catalyzed synthesis of symmetrical diaryl sulfides under ligand free conditions

• K. Harsha Vardhan Reddy,
• V. Prakash Reddy,
• A. Ashwan Kumar,
• G. Kranthi and
• Y.V.D. Nageswar

Beilstein J. Org. Chem. 2011, 7, 886–891, doi:10.3762/bjoc.7.101

• K. Harsha Vardhan Reddy V. Prakash Reddy A. Ashwan Kumar G. Kranthi Y.V.D. Nageswar Organic Chemistry Divison-I, Indian Institute of Chemical Technology, Hyderabad-500 607, India 10.3762/bjoc.7.101 Abstract Potassium thiocyanate acts as an efficient sulfur surrogate in C–S cross-coupling

• reactions mediated by recyclable copper oxide nanoparticles under ligand free conditions. This protocol avoids foul smelling thiols, for the synthesis of a variety of symmetrical diaryl sulfides, via the cross-coupling of different aryl halides with potassium thiocyanate, affording corresponding products in

• moderate to excellent yields. Keywords: aryl halides; aryl sulfides; copper oxide; cross-coupling; ligand free; potassium thiocyanate; recyclable; Introduction After the discovery of copper-promoted Ullmann reaction [1][2][3] for the construction of carbon-hetero atom bonds, several protocols have been

An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals

• Marcus Baumann,
• Ian R. Baxendale,
• Steven V. Ley and
• Nikzad Nikbin

Beilstein J. Org. Chem. 2011, 7, 442–495, doi:10.3762/bjoc.7.57

Kinetics and mechanism of vanadium catalysed asymmetric cyanohydrin synthesis in propylene carbonate

• Michael North and
• Marta Omedes-Pujol

Beilstein J. Org. Chem. 2010, 6, 1043–1055, doi:10.3762/bjoc.6.119

• propylene carbonate under identical reaction conditions to those used in dichloromethane can be explained in two ways. It is possible that in propylene carbonate, some addition of TMSCN to aldehydes occurs exclusively by Lewis base catalysis (using the thiocyanate anion as the Lewis base) and hence is

Aromatic and heterocyclic perfluoroalkyl sulfides. Methods of preparation

• Vladimir N. Boiko

Beilstein J. Org. Chem. 2010, 6, 880–921, doi:10.3762/bjoc.6.88