Indium-mediated cleavage of diphenyl diselenide and diphenyl disulfide: efficient one-pot synthesis of unsymmetrical diorganyl selenides, sulfides, and selenoesters

A convenient and efficient method was developed for the synthesis of alkyl phenyl selenides, sulfides, and selenoesters in one-pot reaction by using indium metal. The reaction showed the selectivity for tert-alkyl, benzylic, and allylic halides over primary and secondary alkyl halides. For the reaction of primary and secondary alkyl iodides and bromides, the yields of selenides were improved by the addition of a catalytic amount of iodine.     

The rapid and efficient synthesis of disulfides from alkyl and acyl halides

Various symmetrical dialkyl and diacyl disulfides are prepared easily in high yields from the corresponding alkyl and acyl halides under mild and nonaqueous conditions using N,N′-dibutyl-N,N,N′,N′-tetramethyl-ethylenediammonium tetrahydroborate (BTMETB) or N,N′-dibenzyl-N,N,N′,N′-tetramethylethylenediammonium tetrahydroborate (BZTMETB) and elemental sulfur. The quaternary diammonium borohydrides were easily prepared by treatment of the corresponding quaternary diammonium chloride or bromide with alkaline solution of sodium borohydride at room temperature. Correspondence: Mahmood Tajbakhsh, Department of Chemistry, Mazandaran University, Babolsar, Iran.     

The rapid and efficient synthesis of disulfides from alkyl and acyl halides

Various symmetrical dialkyl and diacyl disulfides are prepared easily in high yields from the corresponding alkyl and acyl halides under mild and nonaqueous conditions using N,N′-dibutyl-N,N,N′,N′-tetramethyl-ethylenediammonium tetrahydroborate (BTMETB) or N,N′-dibenzyl-N,N,N′,N′-tetramethylethylenediammonium tetrahydroborate (BZTMETB) and elemental sulfur. The quaternary diammonium borohydrides were easily prepared by treatment of the corresponding quaternary diammonium chloride or bromide with alkaline solution of sodium borohydride at room temperature.     

Indium(I) iodide-mediated cleavage of diphenyl diselenide. An efficient one-pot procedure for the synthesis of unsymmetrical diorganyl selenides

A simple and efficient procedure has been developed for the synthesis of unsymmetrical diorganyl selenides through a one-pot indium(I) iodide-mediated reaction of alkyl halide and diphenyl diselenide in methylene chloride at room temperature. [reaction: see text]     

Ruthenium(III) chloride catalyzed efficient synthesis of unsymmetrical diorganyl selenides via cleavage of dibenzyl and diphenyl diselenides in the presence of zinc

[equation: see text] An efficient one-pot route to unsymmetrical diorganyl selenides has been developed by ruthenium(III) chloride catalyzed reactions of dibenzyl or diphenyl diselenides with alkyl halides in the presence of zinc. Organic iodides, bromides, and activated chlorides underwent the reactions efficiently. Unreactive organic chlorides also underwent the same type of selenation with sodium bromide as the additive.     

Efficient synthesis of diorganyl selenides via cleavage of Se-Se bond of diselenides by indium(III) catalyst and zinc

A simple and efficient procedure for the synthesis of unsymmetrical diorganyl selenides from an one-pot indium(III) catalyzed procedure, in the presence of zinc, has been developed. Various organic halides and even the unreactive organic chlorides underwent the reaction efficiently. Also diaryl and dialkyl diselenides underwent the coupling reaction.     

Indium(I) iodide promoted cleavage of diphenyl diselenide and disulfide and subsequent palladium(0)-catalyzed condensation with vinylic bromides. A simple one-pot synthesis of vinylic selenides and sulfides

[reaction: see text] Diphenyl diselenide (and disulfide) undergo facile reaction with indium(I) iodide and the corresponding intermediate complex condenses in situ with a variety of substituted vinyl bromides in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4] in THF at room temperature to produce vinylic selenides and sulfides in good yields. The conversion of (E)-vinyl bromides is remarkably stereoselective giving (E)-vinyl selenides (and sulpfides) whereas the stereoselectivity in reaction of (Z)-vinyl bromides is not very good.     

One-pot efficient synthesis of disulfides from alkyl halides and alkyl tosylates using thiourea and elemental sulfur without contamination by higher polysulfides

An efficient and odorless synthesis of disulfides from alkyl halides using thiourea and elemental sulfur in the presence of sodium carbonate in wet polyethylene glycol (PEG 200) at 40 °C without contamination by higher polysulfides has been developed. This procedure was then extended to preparation of disulfides from alkyl tosylates at 70 °C.     

Indium(I) iodide promoted cleavage of dialkyl/diaryl disulfides and subsequent anti-Markovnikov addition to styrenes: a new route to linear thioethers

The reaction of thiolate anions, generated in situ by indium(I) iodide promoted cleavage of dialkyl/diaryl disulfides, with styrenes has been investigated. Thiolate anions add to a variety of styrenes in an anti-Markovnikov manner producing linear thioethers in high yields. This method provides a new route to the synthesis of thioethers.     

Hydrothiolation of terminal alkynes with diaryl disulfides and diphenyl diselenide: selective synthesis of (Z)-1-alkenyl sulfides and selenides

A simple, stereoselective and efficient method for the hydrothiolation of terminal alkynes with diaryl disulfides and diphenyl diselenide has been developed. In the presence of CuI, rongalite, and Cs₂CO₃, a variety of disulfides underwent the reaction of terminal alkynes stereoselectively to afford the corresponding (Z)-1-alkenyl sulfides in moderate to excellent yields. It is noteworthy that hydroselenations of 1,2-diphenyldiselane with alkynes are also conducted smoothly to afford (Z)-1-alkenyl selenides in good yields under the standard conditions.     

Ligand‐free copper‐catalysed direct synthesis of diaryl sulfides and diaryl disulfides in wet poly(ethylene glycol)

An improved protocol has been developed for the one‐pot CuI‐catalysed preparation of symmetric diaryl sulfides from their available aryl halides in the presence of thiourea as sulfur transfer agent and in the absence of both ligand and organic solvent. This catalytic system was also used for the high‐yielding preparation of diaryl disulfides in the presence of C₂Cl₆ as oxidant.     

One-pot synthesis of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as a sulfur surrogate in the presence of diethylamine catalyzed by copper(I) iodide in polyethylene glycol (PEG200)

A copper catalyzed one-pot protocol for the preparation of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as the sulfur source and diethylamine in polyethylene glycol (PEG200) is described.     

Ligating properties of tertiary phosphine/arsine sulphides or selenides,part V. Complexes of ditertiaryphosphine disulphides and diselenides with platinum(II) and platinum(IV) halides

Summary Platinum(IV)/platinum(II) chloride and bromide form 1 : 1, 1 : 2 or 3 : 2 (metal: ligand) addition compounds with 1,2-ethylene-, 1,3-propylene-and 1,4-butylene-bisdiphenyl-phosphine sulphide or selenide and 1,6-hexamethylene-bisdiphenylphosphine selenide. The adducts have been characterized by elemental analysis, i.r. and reflectance spectra, and molar conductance data. All adducts have been assigned bridged square planar or octahedral arrangements around platinum(II) or platinum(IV) ions respectively. Both oxidation states of platinum conform to class b behaviour with respect to the soft donor sulphur and selenium atoms of the ligands.Reprints of this article are not available.     

An efficient,one‐pot and CuCl‐catalyzed route to the synthesis of symmetric organic disulfides via domino reactions of thioacetamide and aryl (alkyl) halides

In this article, a simple, general and novel method for the synthesis of diaryl (dialkyl) disulfides from aryl (alkyl) halides is described. This is a convenient approach that involves the use of commercially available and inexpensive thioacetamide as a sulfur transfer reagent in the domino process for the synthesis of symmetric organic disulfides. Copyright © 2013 John Wiley & Sons, Ltd.     

Organic reactions in water: an efficient zinc-mediated stereoselective synthesis of (E)- and (Z)-trisubstituted alkenes using unactivated alkyl halides

[reaction: see text] Treatment of the acetyl derivatives of the Baylis-Hillman adducts 3-hydroxy-2-methylene-alkanoates and 3-hydroxy-2-methylene-alkanenitriles with unactivated alkyl halides in the presence of Zn in saturated aqueous NH(4)Cl solution at room temperature afforded (2E)-2-substituted-alk-2-enoates in the first case and (2Z)-2-substituted-alk-2-enenitriles with high (Z)-selectivity in the second case.     

Metal to ligand group transfer reactions : II. Reactions of some π-allylrhodium(I) complexes with trifluoroacetic acid and alkyl,acyl and trimethyltin halides

Rh(π-C₃H₅)(PF₃)₃ (I), reacts with trifluoroacetic acid to form propene and [Rh(CF₃COO)(PF₃)₂]₂ (II). I reacts with t-butyl bromide to give [RhBr(PF₃)₂]₂ and a mixture of propene and 2-methyl-1-propene and with n-propyl bromide to give propene and [RhBr(PF₃)₂]₂. Rh(π-C₃H₅)(PPh₃)₂ (III), and t-butyl bromide yield propene and 2-methyl-1-propene. In these reactions a mechanism involving β-hydrogen abstraction and hydrogen migration via the metal to carbon is proposed. When III reacts with Me₃SnCl the Me₃Sn—moiety migrates intact to the π-allyl group. I reacts with acetyl chloride to give propene, [RhCl(PF₃)₂]₂ and the carbonyl rhodium complex Rh₂Cl₂(PF₃)₃(CO). II does not apparently undergo phosphine ligand exchange unlike the analogous halogeno-bridged dimers.     

A one-pot, efficient, and odorless synthesis of symmetrical disulfides using organic halides and thiourea in the presence of manganese dioxide and wet polyethylene glycol (PEG-200)

Primary, secondary, tertiary, allylic, and benzylic halides are converted efficiently into symmetric disulfides in high yields using thiourea as the sulfur atom source. The reactions are odorless and are performed at 30-35 °C in wet PEG-200 using MnO₂ as an oxidant.     

Acceptor or donor (diaryl B or N) substituted octupolar truxene: synthesis, structure, and charge-transfer-enhanced fluorescence

Two diaryl B- and N-substituted truxene charge-transfer compounds B3 and N3 have been synthesized. The fluorescence intensities of several nonfunctionalized truxene compounds are 1 order of magnitude weaker than that of B3 and N3. To reveal the structure-property correlations, the X-ray structures of B3 and N3 and their precursors 3 and 4 have been determined. The extended molecular dimension, the especially shortened B-C bond, and the improved planarity of B3 can serve as direct structural evidence for the charge transfer.