Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

• of oxidizing systems such as H2O2/aryl benzyl selenoxide and H2O2/diaryl diselenide is similar to that of m-chloroperbenzoic acid [212][232][233]. The main advantage of these selenium-containing systems is that the catalysts are regenerated and can therefore be used at low loadings [234][235][236

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

• as the presence of an o-halogen, an o-selenium, or an o-xanthate, respectively. One of the direct approaches to 2-oxindoles could be a one-electron oxidation of an amide enolate as shown in Scheme 1. Toward this end, in 2009, Kündig and co-workers have developed a novel route to 3,3-disubstituted-2

Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules

• Diego M. Andrada,
• Nicole Holzmann,
• Thomas Hamadi and
• Gernot Frenking

Beilstein J. Org. Chem. 2015, 11, 2727–2736, doi:10.3762/bjoc.11.294

• -selenium adducts, respectively, to determine the π-acceptor strength of the parent NHCs [64][65]. In the same way, Nolan et al. have applied this technique to a wider range of NHCs and have established the connection between the π-accepting abilities and the NMR chemical shift [66]. Furthermore, different

Stereoselective synthesis of hernandulcin, peroxylippidulcine A, lippidulcines A, B and C and taste evaluation

• Marco G. Rigamonti and
• Francesco G. Gatti

Beilstein J. Org. Chem. 2015, 11, 2117–2124, doi:10.3762/bjoc.11.228

• the final products, we deliberately avoided all toxic selenium based reagents [12][13]. We tested several methodologies and the results are summarized in Table 2. In our initial synthesis [9] we applied the hyperiodine chemistry, developed by Nicolaou. However, the o-iodoxybenzoic acid (IBX) mediated

Mechanism, kinetics and selectivity of selenocyclization of 5-alkenylhydantoins: an experimental and computational study

• Biljana M. Šmit,
• Radoslav Z. Pavlović,
• Dejan A. Milenković and
• Zoran S. Marković

Beilstein J. Org. Chem. 2015, 11, 1865–1875, doi:10.3762/bjoc.11.200

• , State University of Novi Pazar, Vuka Karadžića bb, 36300 Novi Pazar, Serbia 10.3762/bjoc.11.200 Abstract The mechanism and selectivity of a bicyclic hydantoin formation by selenium-induced cyclization are investigated. The proposed mechanism involves the intermediates formed by an electrophilic

• addition of the selenium reagent on a double bond of the starting 5-alkenylhydantoin prior the cyclization. These intermediates are readily converted into the more stable cyclic seleniranium cations. A key step of the mechanism is an intramolecular cyclization which is realized through an anti-attack of

• observations. Results and Discussion We have recently reported a three-step reaction sequence to cis-fused bicyclic hydantoins involving selenium-induced cyclization of 5-alkenylhydantoins as the key step [24]. The reaction is chemo- and regiospecific giving only the five-membered bicyclic hydantoins, 5-exo

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• systems which are found in streptorubin B and metacycloprodigiosin [148][149][150]. In this context, the cyclooctene 164 was reacted with the intermediate formed in situ from chloramine-T and elemental selenium [151] and yielded the allylic amine derivative 165 (75%). An N-alkylation with propargyl

Bis(vinylenedithio)tetrathiafulvalene analogues of BEDT-TTF

• Erdal Ertas,
• İlknur Demirtas and
• Turan Ozturk

Beilstein J. Org. Chem. 2015, 11, 403–415, doi:10.3762/bjoc.11.46

• , led to the production of superconducting salts based on TTF type donors containing a heteroatom such as sulfur, selenium, oxygen, etc. [17][18][19][20]. Among a large number of tetrathiafulvalene analogues, bis(ethyleneditiho)tetrathiafulvalene (BEDT-TTF, 3), also known as ET, has been the most

Attempts to prepare an all-carbon indigoid system

• Şeref Yildizhan,
• Henning Hopf and
• Peter G. Jones

Beilstein J. Org. Chem. 2015, 11, 363–372, doi:10.3762/bjoc.11.42

• ): representing the basic cross-conjugated π-electron system of the indigoid compounds [7][8][9]. Whereas the replacement of Y in 2 (X = O) by sulfur and selenium [10][11] or even tellurium [12][13] has been known for some time, derivatives of “phosphaindigo” (Y = various substituted phosphorus derivatives) have

Electrochemical selenium- and iodonium-initiated cyclisation of hydroxy-functionalised 1,4-dienes

• Philipp Röse,
• Steffen Emge,
• Jun-ichi Yoshida and
• Gerhard Hilt

Beilstein J. Org. Chem. 2015, 11, 174–183, doi:10.3762/bjoc.11.18

• and pyran derivatives under indirect electrochemical conditions generating selenium or iodonium cations. The reactions proceed in good yields and regioselectivities for the formation of single diastereomers. Keywords: cyclic ethers; cyclisation; 1,4-dienes; electrochemistry; iodonium; selenium

• in electrochemical reactions using selenium cations. Several methods applying electrochemically generated selenium cations with alkenes or alkynes including seleno-etherification and lactonisation, epoxidation and oxoselenylation sequences have been reported in the last decades [20][21][22][23][24

• ][25][26][27]. The reactions often proceed in a regio- and stereoselective fashion and tolerate a wide range of functionalities. Next to selenium cation induced reactions we put our focus on using halonium cations. The advantage of this type of reaction is its lower toxicity and the easy access towards

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

Come-back of phenanthridine and phenanthridinium derivatives in the 21st century

• Lidija-Marija Tumir,
• Marijana Radić Stojković and
• Ivo Piantanida

Beilstein J. Org. Chem. 2014, 10, 2930–2954, doi:10.3762/bjoc.10.312

• homolytic aromatic substitution of diarylimine (Scheme 3) in respect to the Pd(0)-mediated cyclisation of imidoyl-selenides (Scheme 12) [16]. Authors proposed insertion of a Pd(0) species into the carbon–selenium bond, followed by carbo-palladation onto the phenyl ring. This intermediate then undergoes

Selenium halide-induced bridge formation in [2.2]paracyclophanes

• Laura G. Sarbu,
• Henning Hopf,
• Peter G. Jones and
• Lucian M. Birsa

Beilstein J. Org. Chem. 2014, 10, 2550–2555, doi:10.3762/bjoc.10.266

• Analytical Chemistry, Technical University of Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany 10.3762/bjoc.10.266 Abstract An addition/elimination sequence of selenium halides to pseudo-geminally bis(acetylene) substituted [2.2]paracyclophanes leads to new bridges with an endo-exo-diene

• substructure. The reactions have been found to be sensitive to the substitution of the ethynyl group. The formation of dienes with a zig-zag configuration is related to that observed for non-conjugated cyclic diynes of medium ring size. Keywords: acetylenes; dienes; [2.2]paracyclophane; selenium halides

• between bis(acetylene) 1 and other acetylene derivatives has been reported to provide new π-bridges in [2.2]paracyclophane [14]. Furthermore, a new way for bridging [2.2]paracyclophanes has been accomplished by the addition of selenium monochloride to pseudo-geminally substituted bis(propargylic) alcohols

Magnesium bis(monoperoxyphthalate) hexahydrate as mild and efficient oxidant for the synthesis of selenones

• Andrea Temperini,
• Massimo Curini,
• Ornelio Rosati and
• Lucio Minuti

Beilstein J. Org. Chem. 2014, 10, 1267–1271, doi:10.3762/bjoc.10.127

• and it is considered safer to use in both small- and large-scale reactions [18]. The only disadvantage of MMPP is its poor solubility in non-polar solvents such as dichloromethane. To the best of our knowledge the use of MMPP for the over oxidation of the selenium atom to the corresponding selenone

Simple two-step synthesis of 2,4-disubstituted pyrroles and 3,5-disubstituted pyrrole-2-carbonitriles from enones

• Murat Kucukdisli,
• Dorota Ferenc,
• Marcel Heinz,
• Christine Wiebe and
• Till Opatz

Beilstein J. Org. Chem. 2014, 10, 466–470, doi:10.3762/bjoc.10.44

• the literature. They can be obtained from enones by Michael addition of nitromethane, partial reduction and dehydrogenation of the resulting pyrroline with selenium or sulfur in moderate yields (3 steps) [40][41]. Alternatively, a Nef reaction of the nitromethane adducts gives masked 1,4-dicarbonyls

The Flögel-three-component reaction with dicarboxylic acids – an approach to bis(β-alkoxy-β-ketoenamides) for the synthesis of complex pyridine and pyrimidine derivatives

• Mrinal K. Bera,
• Moisés Domínguez,
• Paul Hommes and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2014, 10, 394–404, doi:10.3762/bjoc.10.37

• compounds. An alternative option for the side chain functionalization of 4- or 6-methyl substituted pyrimidines involves an oxidation with selenium dioxide (Riley oxidation [66][67][68]). To explore the synthetic potential of the newly prepared compounds we exemplarily oxidized bis(pyrimidine) 23a by this

• method in order to finally prepare a macrocyclic compound such as 34 (Scheme 7). Treatment of 23a with an excess of selenium dioxide at 90 °C resulted in the formation of an inseparable mixture of two different aldehydes (probably the dialdehyde and the monoaldehyde). After reduction of the mixture with

Novel supramolecular affinity materials based on (−)-isosteviol as molecular templates

• Christina Lohoelter,
• Malte Brutschy,
• Daniel Lubczyk and
• Siegfried R. Waldvogel

Beilstein J. Org. Chem. 2013, 9, 2821–2833, doi:10.3762/bjoc.9.317

• , (−)-isosteviol can be oxidized under Riley conditions (Table 1, reaction conditions a: selenium dioxide/xylene) [62][63] to give the corresponding diketone 9 [66]. Subsequent esterification with 3,5-dinitrobenzylic chloride under basic conditions (Table 1, reaction conditions b for R = DNB) [67] proceeds with a

The renaissance of organic radical chemistry – deja vu all over again

• Corey R. J. Stephenson,
• Armido Studer and
• Dennis P. Curran

Beilstein J. Org. Chem. 2013, 9, 2778–2780, doi:10.3762/bjoc.9.312

• ][14][15][16], e) radical trifluoromethylation [17] and radical fluorination [18][19][20], f) natural product synthesis [21], g) new main group radical chemistry involving elements like boron [22], phosphorous [23] and selenium [24], tellurium [25], among others, h) synthesis or functionalization of

New syntheses of 5,6- and 7,8-diaminoquinolines

• Maroš Bella and
• Viktor Milata

Beilstein J. Org. Chem. 2013, 9, 2669–2674, doi:10.3762/bjoc.9.302

• treatment of hydrochloride 5 with selenium dioxide in water at room temperature afforded selenadiazoloquinoline 6 in 76% yield (Scheme 2) in comparison with 18% yield obtained by heating of diaminoquinoline 3 with selenium dioxide in dioxane under reflux [9]. To date, pyridoquinoxaline 8 has been prepared

Organocatalyzed enantioselective desymmetrization of aziridines and epoxides

• Ping-An Wang

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

• enantioselectivities were obtained under the reverse ratio of the reagents. Della Sala’s group [47] has demonstrated the first example of a meso-aziridine desymmetrization with selenium nucleophiles to produce chiral β-aminoselenides in high enantioselectivities (up to 99% ee). Surprisingly, when the sterically

Organocatalytic asymmetric selenofunctionalization of tryptamine for the synthesis of hexahydropyrrolo[2,3-b]indole derivatives

• Qiang Wei,
• Ya-Yi Wang,
• Yu-Liu Du and
• Liu-Zhu Gong

Beilstein J. Org. Chem. 2013, 9, 1559–1564, doi:10.3762/bjoc.9.177

• products; selenofunctionalization; Introduction Selenofunctionalization of carbon–carbon double bonds provides practicable opportunities for rapid construction of molecule complexity [1][2][3][4][5][6][7][8], because the versatile carbon–selenium bond could either stabilize carbanions [9][10], serve as a

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

• triphenylbismuthine (2a, 0.5 mmol) were placed in a Pyrex test tube ( = 9 mm) with CHCl3 (4 mL), and the mixture was irradiated by a xenon lamp for 5 h at room temperature. As a result, 0.042 mmol (21% yield based on the amount of selenium atoms) of diphenyl selenide (3aa) was obtained after the isolation by silica

• affords unsymmetrical diaryl selenides in good yields. This method is efficient, because two arylseleno groups from diaryl selenides can be used as a selenium source, and its advantage is that the reaction proceeds in the absence of transition-metal catalysts. Experimental General comments Compounds 1a

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

• sulfur source for the MeSH volatiles, whereas incorporation of labeling from sulfate was not observed. Moreover, the utilization of selenite and selenate salts by marine alphaproteobacteria for the production of methylated selenium volatiles was explored and resulted in the production of numerous

• methaneselenol-derived volatiles via reduction and methylation. The pathway of selenate/selenite reduction, however, proved to be strictly separated from sulfate reduction. Keywords: dimethylsulfoniopropionate; Roseobacter clade; selenium metabolism; sulfur metabolism; volatiles; Introduction The Roseobacter

• -serine to L-cysteine. Elemental sulfur, hydrogen sulfide, or thiosulfate can be funneled via the lithotrophic sulfur oxidation (Sox) pathway to sulfate [18][19][20][21][22]. Analogous degradation steps for the selenium and tellurium derivatives of DMSP (dimethylseleniopropionate, DMSeP, and

Inter- and intramolecular enantioselective carbolithiation reactions

• Asier Gómez-SanJuan,
• Nuria Sotomayor and
• Esther Lete

Beilstein J. Org. Chem. 2013, 9, 313–322, doi:10.3762/bjoc.9.36

• , such as halogen–lithium exchange, tin–lithium exchange, selenium–lithium exchange or reductive lithiation [1][2][3][4][5][6][7][8]. Once the organolithium has been generated, the intramolecular carbolithiation reaction usually takes place with high stereochemical control, as a consequence of a rigid

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

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

• overall yields were very good (78–91%); the relative yields of the three dimers were not determined, however. A monosubstituted bisallene has been prepared by Braverman and co-workers by treatment of the sulfonium or selenium salt 108 with DBU in acetone at 0 °C, providing a mixture of 109 and 110 in a 7

Supramolecular hydrogels formed from poly(viologen) cross-linked with cyclodextrin dimers and their physical properties

• Yoshinori Takashima,
• Yang Yuting,
• Miyuki Otsubo,
• Hiroyasu Yamaguchi and
• Akira Harada

Beilstein J. Org. Chem. 2012, 8, 1594–1600, doi:10.3762/bjoc.8.182

• adding selenium or platinum complexes yields supramolecular assemblies of bis(molecular tube)s cross-linked with the β-CD dimer, which form nanofibers [12][13][14][15]. Moreover, mechanically linked polyrotaxane with the α-CD and poly(ethylene glycol) (PEG) produces a hydrogel material, which exhibits