One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and thiourea

• Mohammad Abbasi and
• Reza Khalifeh

Beilstein J. Org. Chem. 2015, 11, 1265–1273, doi:10.3762/bjoc.11.141

• . On the other hand, the usual methods for preparing thioacids involve the action of toxic and unpleasant smelling, gaseous hydrogen sulfide on carboxylic acid derivatives [46][47]. Also, thioacids as thiols have a strong and repulsive smell. The in situ generation of thioacids using odourless, easy to

A new and convenient synthetic way to 2-substituted thieno[2,3-b]indoles

• Roman A. Irgashev,
• Arseny A. Karmatsky,
• Gennady L. Rusinov and
• Valery N. Charushin

Beilstein J. Org. Chem. 2015, 11, 1000–1007, doi:10.3762/bjoc.11.112

• unequivocally by X-ray crystallography analysis, thus supporting the data of 1H and 13C NMR spectroscopy (Figure 2). The Lawesson’s reagent appears to act firstly as a source of hydrogen sulfide to reduce the C=C double bond in compound 10a, and secondly, as the thiation agent to form thieno[2,3-b]indole 12a by

Design, synthesis and photochemical properties of the first examples of iminosugar clusters based on fluorescent cores

• Mathieu L. Lepage,
• Antoine Mirloup,
• Manon Ripoll,
• Fabien Stauffert,
• Anne Bodlenner,
• Raymond Ziessel and
• Philippe Compain

Beilstein J. Org. Chem. 2015, 11, 659–667, doi:10.3762/bjoc.11.74

• bearing a tetraethylene glycol chain tethered to the boron center via an ethynyl bond proved difficult. The use of copper(I) bromide dimethyl sulfide complex [63] at room temperature led to a complex mixture of products. Better results were obtained with copper(II) sulfate and sodium ascorbate under

On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation

• Andrey S. Mereshchenko,
• Alexey V. Ivanov,
• Viktor I. Baranovskii,
• Grzegorz Mloston,
• Ludmila L. Rodina and
• Valerij A. Nikolaev

Beilstein J. Org. Chem. 2015, 11, 504–513, doi:10.3762/bjoc.11.57

• assumed that the mechanism includes the following steps [12][31][32]: 1,5-electrocyclization of C=S ylide 7’d (step a), 1,3-electrocyclization of C=S ylide 7’d (step b), disproportionation of the thiirane 4’d dimer into thiirane S-sulfide 8’d and alkene 5’d (step c). The subsequent decomposition of

• thiirane-S-sulfide 8’d (step d) and the tetramerization of the extruded S2 molecule results in the formation of the most thermodynamically stable, rhombic modification of sulfur S8 (step e). The obtained computational results for this process are summarized in Table 4 (the data for the Gibbs free energy

• # = 23.8 kcal·mol−1), the thermodynamically more stable alkene 5’d is accumulated in the reaction mixture with time even at room temperature. As for a disproportionation mechanism of two thiirane molecules 4’d (step c) into thiirane S-sulfide 8’d and alkene 5’d, followed by the decomposition of the

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

• Tor E. Kristensen

Beilstein J. Org. Chem. 2015, 11, 446–468, doi:10.3762/bjoc.11.51

• the copper salt with hydrogen sulfide. This methodology has subsequently been employed in a more generic sense as a preparative method for synthesis of acrylic side-chain derivatives of amino acids such as lysine, ornithine, tyrosine and serine [6][7][8], having modified the original technique by

Highly selective electrochemical fluorination of dithioacetal derivatives bearing electron-withdrawing substituents at the position α to the sulfur atom using poly(HF) salts

• Bin Yin,
• Shinsuke Inagi and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2015, 11, 85–91, doi:10.3762/bjoc.11.12

• those of the corresponding sulfides having a single phenylthio group. Although a detailed reason is not clear at present, the additional phenylthio group does not act as an electroauxiliary, but acts as an electron-withdrawing group. As shown in Table 1, the oxidation potentials of sulfide 1g and

Recent advances in the electrochemical construction of heterocycles

• Robert Francke

Beilstein J. Org. Chem. 2014, 10, 2858–2873, doi:10.3762/bjoc.10.303

• has to be carried out at 0 °C in order to stabilize the reactive alkoxysulfonium species. Analogously to Swern- and Moffat-type reactions, this key intermediate is then converted to ketone 8 by quenching with NEt3 at slightly elevated temperatures under elimination of dimethyl sulfide. Alternatively

Expeditive synthesis of trithiotriazine-cored glycoclusters and inhibition of Pseudomonas aeruginosa biofilm formation

• Meriem Smadhi,
• Sophie de Bentzmann,
• Anne Imberty,
• Marc Gingras,
• Raoudha Abderrahim and
• Peter G. Goekjian

Beilstein J. Org. Chem. 2014, 10, 1981–1990, doi:10.3762/bjoc.10.206

• the hexavalent benzene cluster [30], which may be attributed to differences in rigidity and hydrophobicity between the two systems [25]. It thus appears that the direct diaryl sulfide bridge presents a more optimal degree of semi-rigidity. The affinities of the designed glycoconjugates with lecA and

Application of cyclic phosphonamide reagents in the total synthesis of natural products and biologically active molecules

• Thilo Focken and
• Stephen Hanessian

Beilstein J. Org. Chem. 2014, 10, 1848–1877, doi:10.3762/bjoc.10.195

Automated solid-phase peptide synthesis to obtain therapeutic peptides

• Veronika Mäde,
• Sylvia Els-Heindl and
• Annette G. Beck-Sickinger

Beilstein J. Org. Chem. 2014, 10, 1197–1212, doi:10.3762/bjoc.10.118

• modified by fatty acid acylation [97]. The synthesis of these lipidated peptides can be performed by amidation, S- or O-esterification as well as thioether or -sulfide formation. Owing to the strength of the covalent bonds, amidation and O-esterfication are preferred over the other strategies [97

End-group-functionalized poly(N,N-diethylacrylamide) via free-radical chain transfer polymerization: Influence of sulfur oxidation and cyclodextrin on self-organization and cloud points in water

• Sebastian Reinelt,
• Daniel Steinke and
• Helmut Ritter

Beilstein J. Org. Chem. 2014, 10, 680–691, doi:10.3762/bjoc.10.61

• sulfide) containing copolymers is based on the oxidation of thioethers to more hydrophilic sulfoxides or sulfones [11][12]. The specific sulfoxidation of a polymer bound end-group, which is in the focus of our present work, has not yet been investigated. Polymeric materials exhibiting sensitivity to

Direct and indirect single electron transfer (SET)-photochemical approaches for the preparation of novel phthalimide and naphthalimide-based lariat-type crown ethers

• Dae Won Cho,
• Patrick S. Mariano and
• Ung Chan Yoon

Beilstein J. Org. Chem. 2014, 10, 514–527, doi:10.3762/bjoc.10.47

• corresponding polyether side chain containing the lariat-type azacrown ethers 47a–c exclusively (Scheme 11). As observed in earlier studies [34], the initially formed photoproducts undergo in situ dehydration to produce the vinyl sulfide products 46a–c [82]. The photoreactions shown in Scheme 10 and Scheme 11

Carbenoid-mediated nucleophilic “hydrolysis” of 2-(dichloromethylidene)-1,1,3,3-tetramethylindane with DMSO participation, affording access to one-sidedly overcrowded ketone and bromoalkene descendants^§

• Rudolf Knorr,
• Thomas Menke,
• Johannes Freudenreich and
• Claudio Pires

Beilstein J. Org. Chem. 2014, 10, 307–315, doi:10.3762/bjoc.10.28

• the solvent at ≥100 °C through an initial chlorine particle transfer to give a Cl,K-carbenoid. This short-lived intermediate disclosed its occurrence through a reversible proton transfer which competed with an oxygen transfer from DMSO that created dimethyl sulfide. The presumably resultant transitory

• the present “hydrolysis” of 6 became evident when pure dimethyl sulfide (Me2S, boiling point 37 °C) distilled from the reaction vessel into a cold trap during such a preparation of 10. In situ 1H NMR spectra revealed the obligatory formation of ca. one equivalent of Me2S (δH = 2.06 ppm). Small

• derivatives are preferable. “Hydrolysis” of 6, and the KOR/dimsyl-K (11) system. Proposed carbenoid pathway from 6 to acid 10 and dimethyl sulfide (Me2S) in DMSO as the solvent. Proposed pathway to the main side-product 23 formed by nucleophilic addition of 11 to C-2 of 6. Possible course of the carbenoid

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

• Alexander O. Terent'ev,
• Dmitry A. Borisov,
• Vera A. Vil’ and
• Valery M. Dembitsky

Beilstein J. Org. Chem. 2014, 10, 34–114, doi:10.3762/bjoc.10.6

•  83) [336]. The synthesis of the sulfonyl-containing 1,2-dioxane 2-(benzyloxy)-2,6-dimethyl-6-(phenylsulfonylmethyl)-7,8-dioxabicyclo[3.3.1]nonane )297a), included the following steps: oxidation of the sulfide group in 2,6-dimethyl-6-(phenylthiomethyl)-7,8-dioxabicyclo[3.3.1]nonan-2-ol (295) to form

Less reactive dipoles of diazodicarbonyl compounds in reaction with cycloaliphatic thioketones – First evidence for the 1,3-oxathiole–thiocarbonyl ylide interconversion

• Valerij A. Nikolaev,
• Alexey V. Ivanov,
• Ludmila L. Rodina and
• Grzegorz Mlostoń

Beilstein J. Org. Chem. 2013, 9, 2751–2761, doi:10.3762/bjoc.9.309

• . It is well established that the elimination of a sulfur atom S1 from thiirane 8e' has a high positive ΔG value (86.6 kcal·mol−1). It seems that the desulfurization process occurs via the interaction of two molecules of the thiirane, which results in the formation of an intermediate thiirane S-sulfide

Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

• Regina Berg and
• Bernd F. Straub

Beilstein J. Org. Chem. 2013, 9, 2715–2750, doi:10.3762/bjoc.9.308

• in aqueous media is so facile that it even occurs in strongly acidic solutions [117]. Sulfur-based ligands are rarely used for CuAAC catalysis. However, the copper(I) bromide dimethyl sulfide complex [CuBr·SMe2]2 is well soluble in organic media, commercially available and shows good catalytic

Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

• María Martín-Rodríguez,
• Luis M. Castelló,
• Carmen Nájera,
• José M. Sansano,
• Olatz Larrañaga,
• Abel de Cózar and
• Fernando P. Cossío

Beilstein J. Org. Chem. 2013, 9, 2422–2433, doi:10.3762/bjoc.9.280

• ) complexes 3 and 4, identified and characterized by Puddephatt’s group [X = trifluoroacetate (TFA)] [29][30][31], were obtained from NaAuCl4 and dimethyl sulfide and the corresponding amount of the chiral Binap ligand. Finally, the anion interchange was promoted by the addition of an equivalent amount of

Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

• Marcia E. Richard,
• Daniel V. Fraccica,
• Kevin J. Garcia,
• Erica J. Miller,
• Rosa M. Ciccarelli,
• Erin C. Holahan,
• Victoria L. Resh,
• Aakash Shah,
• Peter M. Findeis and
• Robert A. Stockland Jr.

Beilstein J. Org. Chem. 2013, 9, 2002–2008, doi:10.3762/bjoc.9.235

• prepared by displacement of dimethyl sulfide from Me2SAuCl by JohnPhos or t-BuXPhos [23][24]. The (NHC)AuCl (NHC = SIMes, IMes, SIPr, IPr) [19][25] precursors as well as arylgold compounds 1–3 [14] were prepared following literature procedures. The arylboronic acids, alkynes, phenols, and Cs2CO3 (powder

Stereoselective synthesis of the C79–C97 fragment of symbiodinolide

• Hiroyoshi Takamura,
• Takayuki Fujiwara,
• Isao Kadota and
• Daisuke Uemura

Beilstein J. Org. Chem. 2013, 9, 1931–1935, doi:10.3762/bjoc.9.228

• (Scheme 4). The synthesis started from commercially available methyl (S)-3-hydroxy-2-methylpropanoate (21), which was converted to alcohol 22 by the known method [22]. Alcohol 22 was treated with 1-phenyl-1H-tetrazole-5-thiol/DEAD/PPh3 to furnish the corresponding PT-sulfide, which was oxidized with H2O2

Organocatalyzed enantioselective desymmetrization of aziridines and epoxides

• Ping-An Wang

Beilstein J. Org. Chem. 2013, 9, 1677–1695, doi:10.3762/bjoc.9.192

• quinine (OC-7) at room temperature. The β-amino sulfides were obtained in high yields (up to 85%) and with moderate enantioselectivities (up to 72% ee). However, OC-10 and OC-11 afforded extremely disappointing results for desymmetrization and the corresponding β-amino sulfide was obtained nearly racemic

Anodic coupling of carboxylic acids to electron-rich double bonds: A surprising non-Kolbe pathway to lactones

• Robert J. Perkins,
• Hai-Chao Xu,
• John M. Campbell and
• Kevin D. Moeller

Beilstein J. Org. Chem. 2013, 9, 1630–1636, doi:10.3762/bjoc.9.186

• the ketene dithioacetal in the absence of a trapping group [21]. The anodic coupling of a carboxylic acid group with a vinyl sulfide and an enol ether were also examined (Table 2). As with earlier alcohol and amine based cyclizations, reactions with the vinyl sulfide coupling partner proceeded much

• better than did their enol ether counterparts [21][22]. In the previous cases, the argument was made that less polar radical cations underwent better trapping reactions with heteroatomic nucleophiles [23], and a similar argument can be made here. The oxidation potential for the vinyl sulfide used in

• intramolecular electron-transfer to form the carboxy radical can occur, the difference in oxidation potentials suggests that the equilibrium would lie on the side of the oxidized olefin. Styrene substrates and additional insights With the ketene dithioacetal, vinyl sulfide, and enol ether substrates, it appeared

Electron self-exchange activation parameters of diethyl sulfide and tetrahydrothiophene

• Martin Goez and
• Martin Vogtherr

Beilstein J. Org. Chem. 2013, 9, 1448–1454, doi:10.3762/bjoc.9.164

• , diethyl sulfide DES and tetrahydrothiophene THTP, for which we have barred the direct deprotonation at Cα by the choice of a suitable sensitizer; for these substrates, a relayed deprotonation is also impossible because they are not sufficiently basic; however, D•+ can stabilize by dimer formation with

• . As we will show, the activation parameters provide evidence that the observed exchange indeed takes place between dimeric radical cations and D. Results and Discussion On the AM1 level, the heats of formation of D and are −92 kJ/mol and −14 kJ/mol for diethyl sulfide DES as opposed to −69 kJ/mol and

• ]; both in acetonitrile versus SCE) the opposite order, even with a numerically similar difference, is calculated for the radical pair with D•+, although observations [28][29] that for bifunctional donors comprising both an amine and a sulfide moiety photoinduced electron transfer occurs exclusively from

Photoinduced synthesis of unsymmetrical diaryl selenides from triarylbismuthines and diaryl diselenides

• Yohsuke Kobiki,
• Shin-ichi Kawaguchi,
• Takashi Ohe and
• Akiya Ogawa

Beilstein J. Org. Chem. 2013, 9, 1141–1147, doi:10.3762/bjoc.9.127

• excess amounts of either starting substrate were employed, the yields of 3aa increased (Table 3, entries 1, 2 and 5). In the case of the reaction of triphenylbismuthine with diphenyl disulfide (4) instead of diphenyl diselenide, diphenyl sulfide 5 was obtained in lower yield with unidentified byproducts

Appel-reagent-mediated transformation of glycosyl hemiacetal derivatives into thioglycosides and glycosyl thiols

• Tamashree Ghosh,
• Abhishek Santra and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2013, 9, 974–982, doi:10.3762/bjoc.9.112

• halide or acetate with thiourea or thioacetate and hydrolysis of the resulting intermediates [26][27]; (b) reaction of hydrogen sulfide gas with glycosyl halides in hydrogen fluoride [39]; (c) treatment of the glycosyl hemiacetal derivatives with Lawesson’s reagent [40] and (d) treatment of 1,6-anhydro

• sugar derivative [41] and glycosyl trichloroacetimidate derivatives [42] with bis(trimethylsilyl) sulfide. However, most of the reactions have several inherent shortcomings, such as the use of reactive starting materials, longer reaction time, multiple steps, unsatisfactory yield, formation an isomeric

Isotopically labeled sulfur compounds and synthetic selenium and tellurium analogues to study sulfur metabolism in marine bacteria

• Nelson L. Brock,
• Christian A. Citron,
• Claudia Zell,
• Martine Berger,
• Irene Wagner-Döbler,
• Jörn Petersen,
• Thorsten Brinkhoff,
• Meinhard Simon and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2013, 9, 942–950, doi:10.3762/bjoc.9.108

• , Germany 10.3762/bjoc.9.108 Abstract Members of the marine Roseobacter clade can degrade dimethylsulfoniopropionate (DMSP) via competing pathways releasing either methanethiol (MeSH) or dimethyl sulfide (DMS). Deuterium-labeled [2H6]DMSP and the synthetic DMSP analogue dimethyltelluriopropionate (DMTeP

• ]. DMSP is degraded by marine bacteria either under the formation of methanethiol (MeSH) or of dimethyl sulfide (DMS) with a large impact on both the global sulfur cycle and climate [12][13]. DMSP degradation to MeSH starts with the DmdA mediated demethylation to 3-(methylthio)propionate (Scheme 1A) [14

• second obvious candidate as a source for sulfur volatiles is inorganic sulfate, which can be reduced by Roseobacter clade members to hydrogen sulfide via adenylyl sulfate, 3’-phosphoadenylyl sulfate, and sulfite (Scheme 2) [17]. Hydrogen sulfide enters the amino acid pool by reaction with O-acetyl-L