Synthesis and nucleophilic aromatic substitution of 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzene

• Javier Ajenjo,
• Martin Greenhall,
• Camillo Zarantonello and
• Petr Beier

Beilstein J. Org. Chem. 2016, 12, 192–197, doi:10.3762/bjoc.12.21

• fluorination of nitro-substituted diaryl disulfides leading to 3- or 4-nitro-1-(pentafluorosulfanyl)benzenes [7][8][9][10]. This reaction is conducted in tens of kilogram scale in industry. The second method is known as Umemoto’s synthesis and starts with aromatic thiols or diaryl disulfides which are

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• formed aggregates that could be used as nano-containers of drugs. Reduction of the disulfides caused swelling of the aggregates and fast release of incorporated drugs. An early attempt to use dicarboxylic acids with an additional functional group was done by Wallace and Morrow [58]. They used the

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• interest in this functional group. Synthetic methods towards aliphatic SF5-containing compounds are based on free radical addition of SF5Cl or SF5Br to unsaturated compounds [7][8][9], whereas aromatic derivatives are available either by the Umemoto’s two-step synthesis from diaryl disulfides or

• benzenethiols [10][11][12], or by the reaction of nitrophenyl disulfides with elemental fluorine [13][14][15][16]. Aromatic and heteroaromatic SF5 compounds are mostly prepared by the derivatization of commercial nitro-(pentafluorosulfanyl)benzenes [14][17][18][19][20][21][22][23][24][25][26][27] and approaches

Reversibly locked thionucleobase pairs in DNA to study base flipping enzymes

• Christine Beuck and
• Elmar Weinhold

Beilstein J. Org. Chem. 2014, 10, 2293–2306, doi:10.3762/bjoc.10.239

• ][45][46][47][48]. The amino-alkylthiol linker is introduced as its disulfide dimer to protect the sulfur and ensure that the reaction with the convertible nucleobase occurs via the amino group. Two of these residues are placed in adjacent base pairs and reduction of the linker disulfides frees the

Silica: An efficient catalyst for one-pot regioselective synthesis of dithioethers

• Samir Kundu,
• Babli Roy and
• Basudeb Basu

Beilstein J. Org. Chem. 2014, 10, 26–33, doi:10.3762/bjoc.10.5

• employed in asymmetric hydrogenation [18]. Vicinal dithioethers are generally synthesised either by the metal-catalyzed addition of disulfides to alkenes [19][20] or by the traditional nucleophilic substitution of 1,2-dihalides with suitable thiols/thiolates [21][22]. They are also prepared by consecutive

Recent advances in transition metal-catalyzed Csp²-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

• Grégory Landelle,
• Armen Panossian,
• Sergiy Pazenok,
• Jean-Pierre Vors and
• Frédéric R. Leroux

Beilstein J. Org. Chem. 2013, 9, 2476–2536, doi:10.3762/bjoc.9.287

• can be obtained via reaction of trifluoromethylthiolate with an electrophile like aryl halides. On the other hand, they can also be obtained by reacting aryl sulfides or disulfides under nucleophilic or radical conditions with a trifluoromethylation reagent [16][55][124]. Very recently, several

Silica sulfuric acid: a reusable solid catalyst for one pot synthesis of densely substituted pyrrole-fused isocoumarins under solvent-free conditions

• Sudipta Pathak,
• Kamalesh Debnath and
• Animesh Pramanik

Beilstein J. Org. Chem. 2013, 9, 2344–2353, doi:10.3762/bjoc.9.269

• -catalyzed oxidative lactonization or an intramolecular cyclization reaction of δ-ketoaldehydes [12], a ruthenium-catalyzed aerobic oxidative cyclization of aromatic acids with alkynes [13], an FeCl3-promoted regioselective annulation of o-(1-alkynyl)benzoates with disulfides [14], a Heck–Matsuda cyclization

Polymeric redox-responsive delivery systems bearing ammonium salts cross-linked via disulfides

• Christian Dollendorf,
• Martin Hetzer and
• Helmut Ritter

Beilstein J. Org. Chem. 2013, 9, 1652–1662, doi:10.3762/bjoc.9.189

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

• chlorides can be generated by oxidation with aqueous chlorine from a variety of organosulfur species such as thiols, sulfides, disulfides, thioesters, isothiouronium salts, xanthates and thiocyanates [22]. The latter class of organic sulfur compounds seems to be most advantageous, as organic thiocyanates

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

• trimethylsilylthiols in the presence of a Lewis acid (borontrifluoride diethyletherate, stannic chloride, trimethylsilyl trifluoromethanesulfonate, etc.) [15][16][17][18][19][20]. Other methods for the synthesis of thioglycosides include (a) reduction of disulfides using metallic salts [21][22] or nonmetallic reducing

• preparation of several glycosyl donors such as thioglycosides [33][34], glycosyl sulfenamides [35] and sulfonamides [36], glycosyl disulfides [37], glycosyl thionolactones [38], etc. A number of reports are available for the preparation of glycosyl thiols, which include (a) a two-step reaction of glycosyl

Efficient Cu-catalyzed base-free C–S coupling under conventional and microwave heating. A simple access to S-heterocycles and sulfides

• Silvia M. Soria-Castro and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2013, 9, 467–475, doi:10.3762/bjoc.9.50

• disulfides and asymmetric diaryl sulfides in good yields. Keywords: catalysis; copper; cross-coupling; potassium thioacetate; sulfur heterocycles; Introduction Aromatic sulfur compounds including sulfides and heterocycles are relevant in chemical, pharmaceutical and materials industries [1][2][3]. As a

• Method A. Representative procedure for the one-pot three-step synthesis of alkyl aryl sulfides, diaryl disulfides and asymmetric diaryl sulfides The reactions were carried out by using method A. After 24 h at 100 °C, KOt-Bu (1 mmol, 2 equiv) was added to the reaction mixture and stirred for 10 min. The

Synthesis of SF₅-containing benzisoxazoles, quinolines, and quinazolines by the Davis reaction of nitro-(pentafluorosulfanyl)benzenes

• Petr Beier and
• Tereza Pastýříková

Beilstein J. Org. Chem. 2013, 9, 411–416, doi:10.3762/bjoc.9.43

• of SF5 organics is their limited availability. In SF5-aromatics, para- and meta-nitro-(pentafluorosulfanyl)benzenes (3 and 4) (Figure 1) are available by the direct fluorination of the corresponding bis(nitrophenyl)disulfides [18][19][20], and several other SF5-benzenes are available through

Peptoids and polyamines going sweet: Modular synthesis of glycosylated peptoids and polyamines using click chemistry

• Daniel Fürniss,
• Timo Mack,
• Frank Hahn,
• Sidonie B. L. Vollrath,
• Katarzyna Koroniak,
• Ute Schepers and
• Stefan Bräse

Beilstein J. Org. Chem. 2013, 9, 56–63, doi:10.3762/bjoc.9.7

• attachment to other molecules through a variety of functional groups, such as amines (–NH2) and carboxylic acids (–COOH) resulting in peptide bonds, thiols (–SH) resulting in disulfides, thioethers or thioesters, aldehydes (–CHO) and hydroxy (–OH) groups. Nonetheless, coupling to these groups often requires

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

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

Highly selective synthesis of (E)-alkenyl-(pentafluorosulfanyl)benzenes through Horner–Wadsworth–Emmons reaction

• George Iakobson and
• Petr Beier

Beilstein J. Org. Chem. 2012, 8, 1185–1190, doi:10.3762/bjoc.8.131

• aromatic meta- and para-nitro-(pentafluorosufanyl)benzenes (1 and 2) are made by direct fluorination of the corresponding bis(nitrophenyl)disulfides [10][11][12]. A recent report also described a two step synthesis of SF5-benzenes from diaryl disulfides avoiding the use of elemental fluorine [13]. While

Multistep organic synthesis of modular photosystems

• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2012, 8, 897–904, doi:10.3762/bjoc.8.102

• thiols on the surface. Recognition of propagators 3 on the surface of 49 places the strained disulfides of asparagusic acid right on top of the activated thiolates on the surface. Covalent capture by ring-opening disulfide exchange generates new thiolates on the surface of the growing photosystem 55 for

Building photoswitchable 3,4'-AMPB peptides: Probing chemical ligation methods with reducible azobenzene thioesters

• Gehad Zeyat and
• Karola Rück-Braun

Beilstein J. Org. Chem. 2012, 8, 890–896, doi:10.3762/bjoc.8.101

• route to symmetrically and asymmetrically substituted disulfides [21][22][23]. The final cleavage of the Boc-protecting group, the Nα-2-mercaptoethyl auxiliary and the 4,5,6-trimethoxy-2-mercaptobenzyl auxiliary in the 3,4'-AMPB ligation peptides 12 and 14 was successfully achieved with 90% TFA under

Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industry

• Teruo Umemoto,
• Lloyd M. Garrick and
• Norimichi Saito

Beilstein J. Org. Chem. 2012, 8, 461–471, doi:10.3762/bjoc.8.53

• the production of various arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides), from the corresponding diaryl disulfides or aryl thiols. The method consists of two steps: (Step 1) treatment of a diaryl disulfide or an aryl thiol with chlorine in the presence of

• industry. These new methods have been described in patents and patent applications [43][44][45][46][47][48]. Results and Discussion Recently we synthesized various arylsulfur trifluorides (ArSF3) by treatment of diaryl disulfides with chlorine in the presence of potassium [49][50] or cesium fluoride [50

• 13C NMR spectroscopy of the reaction solution. Arylsulfur chlorotetrafluorides were prepared in high yield by the reactions of diaryl disulfides with an excess amount of chlorine (ca. 7 mol or more per mole of the disulfide) in the presence of an excess amount of potassium or cesium fluoride (ca. 16

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

• , hexafluoropropene and alcohols in the presence of KF or CuBr, have been also used for reaction with substituted iodobenzenes (Scheme 27). A variety of perfluoroalkyl- and perfluoroarylcopper mercaptides and selenides have become more accessible, prepared by cleavage of the corresponding disulfides and diselenides

• trifluoromethylthiocopper [106]. Subsequent reaction with aryl halides results in the corresponding trifluoromethylsulfanyl derivatives (Scheme 29). Reduction of bis(perfluoroalkyl)disulfides with tetrakis(dimethylamino)ethylene produces tetrakis(dimethylamino)ethylene dication stabilized perfluoroalkyl thiolates. In

• -phenols, and diaryl disulfides with perfluoroalkyl iodides in liquid ammonia under UV irradiation Kornblum’s work on nucleophilic substitution in alkyl halides [134][135][136][137] and Bunnett’s reactions with non-activated aromatic substrates [138][139][140][141][142] (under UV irradiation) introduced

Synthesis, electronic properties and self-assembly on Au{111} of thiolated (oligo)phenothiazines

• Adam W. Franz,
• Svetlana Stoycheva,
• Michael Himmelhaus and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2010, 6, No. 72, doi:10.3762/bjoc.6.72

• become a groundbreaking strategy in the development of molecular electronics [6]. In recent years, many investigations into SAMs of organic molecules on gold surfaces have been carried out [7]. Thiols, thiol esters, and disulfides can be easily chemisorbed on gold to form SAMs by exposure of well-defined

Synthesis of phosphorothioates using thiophosphate salts

• Babak Kaboudin and
• Fatemeh Farjadian

Beilstein J. Org. Chem. 2006, 2, No. 4, doi:10.1186/1860-5397-2-4

• phosphorothioates has received little attention. The following methods, not generally applicable, have been reported in the literature: (i) reaction of dialkyl phosphites with sulfenyl chlorides,[13] sulfenyl cyanides,[14] thiosulfonates,[15][16] disulfides,[17] and sulfur, [18][19][20][21] (ii) condensation of