Reductive Cleavage of S-S Bond by Samarium Diiodide: A Novel Method for the Synthesis of Disulfides

Samarium diiodide reductively cleaves the S-S bond of sodium alkyl thiosulfates to give the corresponding disulfides in moderate to good yields under mild and neutral conditions.     

Reductive Cleavage of S-S Bond by Samarium Diiodide: Synthesis of β-Thioesters and β-Thionitriles

Theuseofsamariumdiiodideasastrongone-electrontransferreducingandcouplingreagentinorganicsynthesishasgainedincreasingpopularity,especiallyinthepasttenyears1OurpreviousworkonsomedeoxygenationandsomereductivecleavageofSe-SeorTe-TebondwithSmI2wasrepel'te...     

Reductive Cleavage of the S-Si Bond in Phenylthio-trimethylsilane:A Novel Method for the Synthesis of Thiolesters

TheaPPlicationofsamariumdiiodideinorganicSyntilesishasreceivedmoreandmoreattenhoninthelastdecade.'-'Itisapowerfulone-electrontr~ferreducest.Recently,wehaveconsideredthattheS-Stbondmightbereductivelycleavedwithsamariumdiiodide.Thiolestersareusefulintermediatesinorgbocchemistry.'-'Manynewmethodshavebeendevelopedforthepreparationoftlilolestersinrecentyears,'-"forexample,tilereachonbetWeensodiumthiobenzoateandarenediazoniumtetaluoroborates,'beatmentofnitrosoamidesornitroamideswithinercaptansint…     

Novel Reductive Cleavage Reaction of Thiobenzoates with Samarium Diiodide: Convenient Synthesis of Disulfides

The reductive cleavage of thiobenzoates promoted by samarium diiodide afforded various kinds of disulfides in good yields under mild and neutral conditions.     

Simultaneous Reduction of Nitro Group and S-S Bond in Nitrodisulfides by Samarium Diiodide: A New Approach to Benzothiazolines

Asapowerfulandversatileone-electrontransferreductant,Sml,hasbeenappliedwidelyinorganicsynthesis'.OurpreviousworksonthereductionofnitrocompoundsandreductivecleavageofS-S,Se-Se,Te-TebondswithSml,'ledustoinvestigatethesimultaneousreductionofnitrogroupandS-SbondbySml,.Benzothiazolinesderivativesareimportantreagentsandusefulintermediatesinorganicsynthesisandpharmaceuticalchemistry.Forinstance,theycanbeusedasadditionagentsforphotographicemulsions",effectiveacaricides",antituberculousagents",lubr…     

含水四氢呋喃中二茂钛全氟辛基磺酸配合物催化锌粉还原二硫醚及其在合成硫代酸酯中的应用

以含水四氢呋喃作溶剂,室温下,在5.0 mol％二茂钛全氟辛基磺酸配合物催化下,锌粉可以有效地还原断裂S-S键,形成亲核性的硫负离子与酸酐(α-溴代羰基化合物)反应,高产率得到对应硫代酸酯(α-硫代羰基化合物).讨论了反应机理.     

Facile Synthesis of Amidines via Intermolecular Reductive Coupling of Nitriles with Azobenzene Promoted by Samarium Diiodide

SinceintroducedbyKaganandhisgroups',Sml,hasbeenextensivelyinvestigatedasamild,neutral,selectiveandversatilesingIeelectrontransferreductantinsyntheticchemistry=.Suchas,Barbierreactions,Reformatskyreactions,pinacolcouplingandketone-oIefinreductivehavebeenreportedusingSmI,asreagent.Thereactivitiesofvariousnitrogenfunctionalgroups(imine,oxime,nitro,azo,cyano)towardsSmI,havealsobeenexamined.Recently,ourgrouphasreportedtheintermolecularreductivecouplingofnitrogroupswithcyanogroupsinducedbySml='.…     

Synthesis of Aminomethyl Arylsulfides via Novel Synthetic Auxiliary Benzotriazole Promoted by Samarium Diiodide

Benzotriazolemethodologyhasalreadycomealongway,butinthelastdecadebenzotriazoleisanexcellentsyntheticauxiliaryinmanyusefulsynthetictransformationsl-5.Becausebenzotriazolateanionisagoodleavinggroup,itmaybeusedinplaceofahalogeninmanyreactions.Theuseofbenzotriazoleasasyntheticauxiliaryhasanumberofsignificantadvantages.Forexample,itisreadilyavailableandquitecheap;itisacidicwithapKaofabout8,whichenableseasyseparationandrecovery.Manytypesofcompoundshavebeensynthesizedviabenzotriazoleauxifiary>.Samar…     

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

Reactions proceeding through open-shell, single-electron pathways offer attractive alternative outcomes to those proceeding through closed-shell, two-electron mechanisms. In this context, samarium diiodide (SmI(2) ) has emerged as one of the most important and convenient-to-use electron-transfer reagents available in the laboratory. Recently, significant progress has been made in the reductive chemistry of other divalent lanthanides which for many years had been considered too reactive to be of value to synthetic chemists. Herein, we illustrate how new samarium(II) complexes and nonclassical lanthanide(II) reagents are changing the landscape of modern reductive chemistry.     

钐－二氯二茂钛体系促进的碳－硫键的还原断裂－二烷基二硫醚的合成

A mild and rapid method was found for the reductive cleavage of the carbon-sulfur bond in the alkylthiocyanates by samarium/Cp2TiC12 system to give the corresponding dialkyl disulfides in moderate to good yields.     

Reductive Cleavage of the Se-Se Bond by the Sm-CdCl_2-HMPA System: A New One-Pot Method for the Synthesis of Selenoesters

Organoseleniumcompoundshaveattractedconsiderableinterestasusefulsyntheticreagentsandintermediatesinorganicsynthesis'.Therearemanymethodsforthesynthesisofselenoesters,whichincludethereductionofthediselenidewithsamariumdiiodide',lithiumaluminiumhydride',etc.Here,wewishtoreportanewmethodforthepreparationoftheactivecadmiumreagentinsitufromSin/CdCI,/HMPAsystem.Itreactswithdiselenidestogeneratecadmium(II)selenolatesandthencadmium(II)selenolatesreactwithacidchloridesandacidanhydridestogiveseleno…     

Synthesis of Functionalized 2,3-Dihydropyrroles Promoted by Samarium Diiodide

Abstract

The intermolecular reductive coupling of 1,1-diaryl-2,2-dicyanoethylenes or 1,1-diaryl-2-cyano-2-ethoxycarbonylethylenes with substituted benzalazines induced by samarium diiodide was studied. Functionalized 2,3-dihydropyrroles were prepared in good yields under neutral and mild conditions.     

Zn/ ZrCl_4 System Induced Reductive Cleavage of Se-Se Bond in Diaryl Diselenides: A Novel Method for the Systhesis of Selenoesters

In recent years, organoselenium compounds have been extensively used as important synthetic reagents and intermediates in organic synthesis1-3. Among them, selenoesters are very useful intermediates in the synthesis of natural compounds4. While there are many methods for the synthesis of selenoesters, the most common approach is the use of selenide anions reacting with acylation reagents. Selenide anions can be obtained by cleavage of diselenides with sodium in liquid ammonia5 or in THF/H…     

Stereoselective Syntheses of Bridgehead Hydroxy Compounds via Reductive Cyclization Reactions Promoted by Samarium Diiodide

Cycloalkanones appended with an α, β-unsaturated carbonyl side chain react with 2.25 equivalents of samarium diiodide to form bicyclic or tricyclic bridgehead hydroxy compounds stereoselectively in moderate yield.     

Disulfide Bond Cleavage: A Redox Reaction Without Electron Transfer

By using Car–Parrinello molecular dynamics (CPMD) simulations we have simulated a mechanically induced redox reaction. Previous single‐molecule atomic force microscopy (AFM) experiments demonstrated that the reduction of disulfide bonds in proteins with the weak reducing agent dithiothreitol depends on a mechanical destabilization of the breaking bond. With reactive molecular dynamics simulations the single steps of the reaction mechanism can be elucidated and the motion of the electrons can be monitored. The simulations show that the redox reaction consists of the heterolytic cleavage of the S? S bond followed by a sequence of proton transfers.     

Cleavage of Se-Se Bond by Sm/cat. CoCl2 System: A Novel Method for the Synthesis of Selenoesters

The Sm/cat. CoCl₂ system promoted diselenides to react with anhydrides or acyl chlorides to afford selenoesters in good yield under mild and neutral conditions.     

Reduction of Elemental Selenium by Samarium Diiodide: the Synthesis of Dithiodiselenides and Dithioselenides

Selenium is an essential element in living organism. It is reported that the selenosulfides have been transported in vivo in glutathione or coenzyme-A1. It is also discovered in low concentration in garlic2. In organic synthesis, selenosulfides are useful intermediates3. Several methods for the formation of sulfur-selenium bond have been reported. For example, the compounds including S-Se bond were prepared by chloroamination of thiols and selenols4; by heating the selenocyanate with thiols5…     

二碘化钐在有机合成中的应用新进展

综述了2005年以来二碘化钐在有机合成中应用的新进展,主要涉及二碘化钐在还原偶联反应以及作为预催化剂方面的一些新的应用.