Tailoring of organic dyes with oxidoreductive compounds to obtain photocyclic radical generator systems exhibiting photocatalytic behavior

• Christian Ley,
• Julien Christmann,
• Ahmad Ibrahim,
• Luciano H. Di Stefano and
• Xavier Allonas

Beilstein J. Org. Chem. 2014, 10, 936–947, doi:10.3762/bjoc.10.92

• ]. Hydrogen donor coinitiators could be amines [33][34][35][36][37][38], ethers [39][40], sulfides [41][42][43] or thiols [43][44][45]. Electron transfer coinitiators could be borate salts [46][47], iodonium [48][49] or triazine [32] derivatives. However, if Type II PIS gain sensitivity in the visible part of

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

Reaction of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithiethane with N-vinyl compounds

• Viacheslav A. Petrov and
• Will Marshall

Beilstein J. Org. Chem. 2013, 9, 2615–2619, doi:10.3762/bjoc.9.295

• sulfides, cyclic dienes and styrenes [1][2], fluoride anion-catalyzed reactions of compound 1 with vinyl ethers [1][3][4], vinyl sulfides [3], ketene dimethylacetal [5], styrenes [6][7], cyclic dienes [8] and quadricyclane [9]. At this point, no data for the reaction of HFTA or HFTA dimer with vinylamines

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

• ]. In the same paper, the authors showed that cobalt perchlorate could also improve the yield of the uncatalyzed reaction. Iron sulfate, on the other hand, gave the same yield as in the absence of added metals. 4 Catalytic trifluoromethylthiolation Aryl trifluoromethyl sulfides (ArSCF3) play an

• stability of molecules in acidic medium. One can place this substituent next to the ever-present CF3 and the emerging OCF3 substituent [55][56][130]. In contrast, aryl trifluoromethyl sulfides are key intermediates for the preparation of trifluoromethyl sulfoxides or sulfones. Aryl trifluoromethyl sulfides

• 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

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

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

• their radical cations, which were generated by photoinduced electron transfer from the sulfides to excited 2,4,6-triphenylpyrylium cations, was investigated by time-resolved measurements of chemically induced dynamic nuclear polarization (CIDNP) in acetonitrile. The strongly negative activation

• solvent reorganization. Keywords: CIDNP; electron transfer; free radicals; kinetics; photochemistry; pyrylium salts; self-exchange; sulfides; Introduction Single-electron transfer is probably the simplest chemical process of an organic molecule, because usually no full bonds are broken or formed. For

• reaction into a hydrogen abstraction. In a previous report on two aliphatic amines [20], we have used time-resolved CIDNP experiments to distinguish between the ensuing electron and hydrogen self-exchanges of D•+ and . In the present work, we investigate two structurally similar aliphatic sulfides

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

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

• microwave irradiation the time was drastically reduced to 2 h. Both procedures are simple and involve a low-cost catalytic system. This methodology was also applied to the “one-pot” synthesis of target heterocycles, such as 3H-benzo[c][1,2]dithiol-3-one and 2-methylbenzothiazole, alkyl aryl sulfides, diaryl

• 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

• diverse heterocycles containing sulfur atoms by intra- [42][43][44] and intermolecular [45][46][47] reactions. Aryl thioesters are versatile intermediates for the synthesis of a variety of sulfur compounds including aryl thiols, aryl alkyl sulfides, aryl sulfenyl chlorides, aryl sulfonyl chlorides [48

Stereoselective synthesis of tetrasubstituted alkenes via a sequential carbocupration and a new sulfur–lithium exchange

• Andreas Unsinn,
• Cora Dunst and
• Paul Knochel

Beilstein J. Org. Chem. 2012, 8, 2202–2206, doi:10.3762/bjoc.8.248

• due to steric hindrance and proceeds only if electron-withdrawing groups are attached to the alkyne unit to facilitate the carbometalation step. Recently, we studied the chemistry of alkenyl sulfides and their use for carbometalation extensively [13]. Therefore, we envisioned using an alkynyl

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

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

Facile synthesis of functionalized tetrahydroquinolines via domino Povarov reactions of arylamines, methyl propiolate and aromatic aldehydes

• Jing Sun,
• Hong Gao,
• Qun Wu and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2012, 8, 1839–1843, doi:10.3762/bjoc.8.211

• dienophiles, vinyl enol ethers, vinyl enamides, vinyl sulfides, cyclopentadienes, indenes, alkynes and enamines have been mostly used in this method [12][13][14][15][16][17][18][19][20][21][22]. β-Enamino esters [23][24][25][26], which may be readily generated in situ by the addition of a primary amine to

Carbamate-directed benzylic lithiation for the diastereo- and enantioselective synthesis of diaryl ether atropisomers

• Abigail Page and
• Jonathan Clayden

Beilstein J. Org. Chem. 2011, 7, 1327–1333, doi:10.3762/bjoc.7.156

• ], sulfides and sulfones [13], and many of the methods we developed for their asymmetric synthesis employed dynamic resolution techniques under kinetic or thermodynamic control [6][11][13][14][15][16]. The mechanistic possibilities associated with dynamic resolution were initially elaborated by Beak for

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

• 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

• reported over the years to establish C–N, C–O, and C–S linkages. Carbon–sulfur bonds are widespread, occurring in numerous pharmaceutically and biologically active compounds [4][5][6][7][8]. A large variety of aryl sulfides are in use for diverse clinical applications in the treatment of cancer [9], HIV

Solvent- and ligand-induced switch of selectivity in gold(I)-catalyzed tandem reactions of 3-propargylindoles

• Estela Álvarez,
• Delia Miguel,
• Patricia García-García,
• Manuel A. Fernández-Rodríguez,
• Félix Rodríguez and
• Roberto Sanz

Beilstein J. Org. Chem. 2011, 7, 786–793, doi:10.3762/bjoc.7.89

• esters have been extensively investigated. In these processes the gold-carbenoid species generated are able to undergo a wide variety of further transformations [8][9][10][11]. In addition, propargylic sulfides have also been reported as useful substrates for this type of process, participating in

Alkene selenenylation: A comprehensive analysis of relative reactivities, stereochemistry and asymmetric induction, and their comparisons with sulfenylation

• Vadim A. Soloshonok and
• Donna J. Nelson

Beilstein J. Org. Chem. 2011, 7, 744–758, doi:10.3762/bjoc.7.85

• -chloroalkyl aryl sulfides and selenides, respectively. Conversely, differences between the two reactions have been reported, but the sources of these differences have not been fully explained: While arenesulfenyl chlorides add to alkenes with an anti-Markovnikov orientation, areneselenenyl chlorides add with

Asymmetric synthesis of tertiary thiols and thioethers

• Jonathan Clayden and
• Paul MacLellan

Beilstein J. Org. Chem. 2011, 7, 582–595, doi:10.3762/bjoc.7.68

• , sulfimines and sulfilimines [9]. Chiral sulfoxides and sulfonium ylids have themselves been extensively used as tools for asymmetric synthesis [3]. With regard to chiral sulfur(II) compounds – namely thiols and thioethers (sulfides) with chirality at carbon – methods available for their asymmetric

The allylic chalcogen effect in olefin metathesis

• Yuya A. Lin and
• Benjamin G. Davis

Beilstein J. Org. Chem. 2010, 6, 1219–1228, doi:10.3762/bjoc.6.140

• hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowed the first

• . Keywords: allyl substituent effect; allyl sulfides; aqueous chemistry; olefin metathesis; protein modifications; Review Olefin metathesis is one of the most useful chemical transformations for forming carbon–carbon bonds in organic synthesis (Scheme 1) [1][2][3][4]. The broad utility of olefin metathesis

• substrates [27][28]. The effect of other allylic chalcogens in olefin metathesis Allyl sulfides are privileged substrates in olefin metathesis While there are many examples of allylic alcohols and ethers in metathesis, examples with allyl sulfide substrates were until recently noticeably few. This 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

• Vladimir N. Boiko Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanskaya St. 5, 02094 Kiev, Ukraine 10.3762/bjoc.6.88 Abstract This review covers all of the common methods for the syntheses of aromatic and heterocyclic perfluoroalkyl sulfides, a class of compounds

• -process; perfluoroalkylation; perfluoroalkyl sulfides; SRF-introduction; Review 1. Introduction Perfluoroalkyl sulfides of aromatic and heterocyclic compounds have been an important aspect in the general development of organofluorine chemistry over the last twenty years. Alkyl aryl sulfides containing

• partly fluorinated aliphatic moieties have been widely used for a number of years. Their methods of preparation, for example, by the reaction of thiols with fluoro-olefins or with chloropolyfluoroalkanes are well known and have been widely used. In contrast, sulfides with fully fluorinated aliphatic

CAAC Boranes. Synthesis and characterization of cyclic (alkyl) (amino) carbene borane complexes from BF₃ and BH₃

• Julien Monot,
• Louis Fensterbank,
• Max Malacria,
• Emmanuel Lacôte,
• Steven J. Geib and
• Dennis P. Curran

Beilstein J. Org. Chem. 2010, 6, 709–712, doi:10.3762/bjoc.6.82

• , sulfides, etc.), NHC–borane complexes are highly stable in diverse environments. Complexes such as those shown in Figure 1 are white solids that can often be chromatographed if desired. Many such complexes resist decomplexation, oxidation, and both acidic and basic hydrolysis. Such NHC–boranes are

Shelf-stable electrophilic trifluoromethylating reagents: A brief historical perspective

• Norio Shibata,
• Andrej Matsnev and
• Dominique Cahard

Beilstein J. Org. Chem. 2010, 6, No. 65, doi:10.3762/bjoc.6.65

• . (trifluoromethyl)dibenzoheterocyclic salts with electron-donating and electron-withdrawing substituents in benzene rings for fine tuning of their electrophilicity [12][13][14]. (Trifluoromethyl)dibenzothio- and selenophenium salts 5 and 6, respectively, were synthesized either by oxidation of the starting sulfides

The development and evaluation of a continuous flow process for the lipase- mediated oxidation of alkenes

• Charlotte Wiles,
• Marcus J. Hammond and
• Paul Watts

Beilstein J. Org. Chem. 2009, 5, No. 27, doi:10.3762/bjoc.5.27

• found widespread application in the conversion of nitriles to amides [32], aldehydes to acids [33], and sulfides to sulfones [34]. To enable comparison of the method developed here with batch investigations previously conducted, the oxidation of 1-methylcyclohexene (6) to 1-methylcyclohexene oxide (7

Enantiospecific synthesis of [2.2]paracyclophane- 4-thiol and derivatives

• Gareth J. Rowlands and
• Richard J. Seacome

Beilstein J. Org. Chem. 2009, 5, No. 9, doi:10.3762/bjoc.5.9

• ]paracyclophane compounds; aryl sulfonylation and the related sulfenylation facilitates the synthesis of sulfonic acids, sulfonamides and protected thiols [24][25][26] whilst directed metallation has allowed the formation of various sulfides [27][28][29][30]. Very few methodologies allow the synthesis of simple

• of enantiomerically pure 4-hydroxy[2.2]paracyclophane or application of our own sulfoxide-metal exchange protocol [31] would permit enantiospecific variants of either route, but neither has been reported. An elegant entry to a variety of racemic alkyl sulfides and sulfoxides by an SEAr reaction

Efficient 1,4-addition of α-substituted fluoro(phenylsulfonyl)methane derivatives to α,β-unsaturated compounds

• G. K. Surya Prakash,
• Xiaoming Zhao,
• Sujith Chacko,
• Fang Wang,
• Habiba Vaghoo and
• George A. Olah

Beilstein J. Org. Chem. 2008, 4, No. 17, doi:10.3762/bjoc.4.17

• course. Reaction mechanism for phosphine catalyzed 1,4-addition to α,β-unsaturated compounds. Oxidation of sulfides and monofluorination of sulfones. PMe3-catalyzed reaction of fluoro(phenylsulfonyl)-substituted methane derivatives with methyl vinyl ketone and ethyl acrylate. K2CO3/DMF catalyzed 1,4

Synthesis of sulfonimidamides from sulfinamides by oxidation with N-chlorosuccinimide

• Olga García Mancheño and
• Carsten Bolm

Beilstein J. Org. Chem. 2007, 3, No. 25, doi:10.1186/1860-5397-3-25

• 3f was isolated in only moderate yield (50%), together with unreacted sulfonimidoyl chloride 2a (28%), even after prolonged reaction times (24 h). The weakly basic cyanogen amine (pKa ~ 17), which had previously been used in the formation of N-cyano sulfilimines from sulfides using NBS as