Synthesis of α-Benzotriazole Sulfides Promoted by Samarium Diiodide

1-(Benzotriazol-1-yl) unsymmetrical diorganyl sulfides were synthesized via replacement of chlorine atom in 1-(benzotriazol-1-yl)-1-chloromethane with thiolate anions promoted by SmI₂.     

β-Diketone Synthesis by Reaction of α-Haloketones with Acid Chlorides or Acid Anhydrides Promoted by Samarium Triiodide

Promoted by SmI₃, α-haloketones were reacted with acid chlorides or acid anhydrides and β-diketones were synthesized via intermediate samarium enolates.     

Synthesis of α-Benzotriazole Selenides and Tellurides Promoted by Samarium Diiodide

1-(Benzotriazol-1-yl) unsymmetrical diorganyl selenides and tellurides were synthesized via replacement of chlorine atom in 1-(benzotriazo-l-yl)-l-chloromethane with selenolate and tellurolate anions promoted by SmI₂.     

Temperature-Controlled Stereodivergent Synthesis of 2,2′-Biflavanones Promoted by Samarium Diiodide

In this work, the first example of a radical stereodivergent reaction directed towards the stereoselective synthesis of both (R*,R*)- and (R*,S*)-2,2′-biflavanones promoted by samarium diiodide is reported. Control experiments showed that the selectivity of this reaction was exclusively controlled by the temperature. It was possible to generate a variety of 2,2′-biflavanones bearing different substitution patterns at the aromatic ring in good-to-quantitative yields, being both stereoisomers of the desired compounds obtained with total or high control of selectivity. A mechanism that explains both the generation of the corresponding 2,2′-biflavanones and the selectivity is also discussed. The structure and stereochemistry determination of each isomer was unequivocally elucidated by single-crystal X-ray diffraction experiments.     

Cyclodimerization of α, β-Unsaturated Ketones Promoted by Samarium Diiodide

Samarium (II) iodide has been successfully utilized as a strong one-electron transfer reducing agent for the cyclodimerization of α, β-unsaturated ketones. The absence of any alcohol as proton source is essential. The reaction is regioselective over the competitive carbon-carbon double bond reduction and stereocontrolled. The configuration of the cyclodimerization products, has been confirmed by X-ray analysis.     

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…     

A Facile Route to Convert Acetylacetone into Other β-Diketones with Acyl Chlorides Promoted by Samarium Triiodide

Reaction of acetylacetone with acyl chlorides in the presence of SmI₃ gave β-diketones RCOCH₂COCH₃ (I) or RCOCH₂COR (II) in good yields under mild and neutral conditions.     

Synthesis of New Nitroamino-Containing 1,2,4-Triazines by Reaction of 1-Amino-2-nitroguanidine with α-Diketones

The reaction of 1-amino-2-nitroguanidine with α-diketones (butane-2,3-dione and 1,2-diphenylethanedione) produced new specimens of nitroamino-containing 1,2,4-triazines. The structure of the synthesized compounds of linear and heterocyclic series was confirmed by ¹H, ¹³C{¹H} NMR, IR, and UV spectra.     

A New Approach to 2,3-Dihydro-1H-1,5-Benzodiazepines from the Reaction of o-Nitrophenylazide with α,β-Unsaturated Ketones Promoted by Samarium Diiodide

Applications of samarium diiodide as a mild, neutral, selective and versatile single-electron transfer reducing and coupling reagent in organic synthesis have grown significantly in the last decade1. It is well known that both nitro compounds2a and azide compounds2b can be easily reduced by SmI2 to the corresponding amines. Little attention has been given to the intermediates derived from nitro or azide groups by treatment of SmI2, which may lead to reactions difficult to accomplish by other …     

The Reductive Addition Reaction of Substituted 2-Chloromethyl-1, 3, 4-oxadiazole to Aldehydes and Ketones Promoted by Samarium Diiodide

1-（β-Hydroxyalkyl）-l,3,4-oxadiazole derivatives were synthesized via reductive addition reactions of 2-chloromethyl-l,3,4-oxadiazole with carbonyl compounds under mild conditions promoted by SmI2.     

Synthesis of α-Amino Unsymmetrical Diorganyl Selenides via Novel Synthetic Auxiliary Benzotriazole Promoted by Samarium Dhodide

α -Amino unsymmetrical diorganyl selenides are synthesized through nucleophilic substitution of a benzotriazolate anion by selenolates promoted by samarium diiodide.     

The Reaction of Thioacids with α-Haloketones in Water: an Environmentally Green Synthesis of Thioester Derivatives

Abstract

The reaction between a thioacid and an α-haloketone in water affords thioester derivatives in high yields. The reaction proceeded smoothly and cleanly under mild conditions and no side reactions were observed.     

Synthesis of α-Halogenated Imidoyl Cyanides1

As part of our investigations in the field of the α-halogenated imine chemistry,¹ we describe herein a convenient and general synthesis of aliphatic α-halogenated imidoyl cyanides 1 (X=Cl,Br). From the synthetic and mechanistic point of view, compounds 1 are expected to exhibit interesting features due to the presence of three functional groups in the molecule.     

Reaction of α-bromolevoglucosenone with 2,2-disubstituted 1,3-dinitropropanes

2,2-Bis(nitromethyl)decane and 4-methyl-2,2-bis(nitromethyl)pentane reacted with α-bromolevoglucosenone in the presence of a base under ultrasonic treatment to give the corresponding cyclopenta-fused derivatives. Analogous reactions of 1,1-bis(nitromethyl)cycloalkanes with α-bromolevoglucosenone afforded spiro compounds.     

Synthesis of α,β-Unsaturated Nitriles from the Iodine Catalyzed Reaction of Chloroacetonitrile with Aldehydes Promoted by Tri-n-Butylarsine and Magnesium

α,β-Unsaturated nitriles were synthesized from the iodine catalyzed reaction of chloro-acetonitrile with aldehydes promoted by tri-n-butylarsine and magnesium.     

Stereoselective Michael Addition and Michael-aldol Tandem Reaction of Diorganyl Diselenides or Disulfides with Conjugated Alkynones Mediated by Samarium Diiodide

Stereoselective Michael addition and Michael-aldol tandem reaction of diorganyl diselenides and disulfides with conjugated alkynones mediated by samarium diiodide were studied. The reaction temperature was critical for the stereoselectivity, β-Organylselenoalkenones or β-organylthioalkenones and γ-organylselenoallylic alcohols or γ-organylthioallylic alcohols were prepared in good yields.     

Substitution of Acyl for Acetyl with N‐Acylbenzotriazoles Catalyzed by Samarium Triiodide

Catalyzed by samarium triiodide (SmI₃), substitution of acyl with N‐acylbenzotriazoles for acetyl in acetoacetic esters and acetylacetone proceeds smoothly under neutral conditions in open air, affording the corresponding β‐keto esters and β‐diketones in good yields.     

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

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

Synthesis of 5‐Cyano‐1,3‐dioxoalkanes by Reaction of 1,3‐Dicarbonyl Dianions with Bromoacetonitrile

5‐Cyano‐1,3‐dioxoalkanes were prepared by reaction of 1,3‐dicarbonyl dianions with bromoacetonitrile.