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

The reduction of disulfides by samarium diiodide led to sa arium thiolates (ArSSml2).This new thiolate anion species reacted smoothly with α, β -unsaturated esters (nitriles) to give 1,4-addition products β -thioesters and β -thionitriles in good yields under mild and neutralcondition.

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

Aminomethyl arylsulfides are synthesized through nucleophilic substitution of a benzotriazolate anion by thiolates promoted by samarium diiodide.

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

o-Nitrophenylazide was reduced by SmI2 in anhydrous THF at room temperature to produce active intermediate 2 (samarium amide), "living" double-anion in situ which reacted smoothly with α，β-unsaturated ketones to afford 2,3-dihydro-1H-1,5-benzodiazepines 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

Nitrodisulfides were reduced by SmI2/HMPA in anhydrous THF at room temperature to produce active intermediates (samarium thiolates and amides), which were 'living' double-anions and reacted smoothly with aldehydes or ketones to afford benzothiazolines in good yields under mild and neutral conditions.

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.

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

The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se-2(2-) and Se2-), these nucleophilic species reacted readily with sodium alkyl thiosulfates to afford dithiodiselenides and dithioselenides in moderate to good yield under mild conditions.

Samarium Diiodide-Induced Reductive Cleavage of Se-St Bond in Arylselenotrimethylsilane Leading to the Formation of Samarium Arylselenolate: Synthesis of β-Arylseleno Estsrs and β-Arylseleno Nitriles

The Se-St bond in arylselenotrimethylsilane was reduced by samarium diiodide to produce samarium arylselenolate, which reacted with a,β-unsaturated esters or α,β-unsaturated nitriles to give β-selenoesters and β-selenonitriles, respectively.

A Novel Synthesis of 3,4-DihydrO-(2H)-1,2,4-Benzothiadiaizine-1,1-Dioxides Promoted by Samarium Diiodide

Dihydro-(2H)-1 .2.4-benzothiadizine-1. 1-dioixdes were prepared in good yields via reductive cyclization of o-nitrobenzenesulfonamidcs with aldchydes promoted by Sml2 under mild and neutral condition.

Samarium Diiodide-Mediated Reductive Cleavage of Se-Se Bond of Diacyl Diselenides:A New Method for Synthesis of β-Selenoesters

The reduction of diacyl diselenides by samarium diiodide led to the production ofsamarium acylselenolates, which reacted with a,β-unsaturated esters or nitriles to give β-selenoesters or selenonitriles under mild and neutral conditions.

Samarium Diiodide Catalyzed Synthesis of 2,3-Dihydro-1 H-benzo[b][1,4]-diazepine Derivatives

Samarium diiodide （SmI2） was found to be an efficient catalyst for the condensation of o-phenylenediamine and ketones to afford the corresponding 2,3-dihydro-1H-benzo[b][1,4]-diazepines in moderate to excellent yields under very mild and solvent-free conditions. The real active species here was suggested to be a Sin（Ⅲ） intermediate formed in situ and the mechanism of the present reaction was proposed.

Stereoselective Michael Addition and Michael-aldol Tandem Reaction of Diorganyl Diselenides or Disulfides with Conju-gated 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. -Organylselenoalkenones or -organylthioalkenones and ?-organylselenoallylic alcohols or ?-organylthioallylic alcohols were prepared in good yields.

Samarium diiodide induced asymmetric synthesis of γ-butyrolactone using chiral auxiliaries derived from isosorbide and isomannide

The asymmetric reductive coupling reaction of various acrylates derived from D-isosorbide and D-isomannide with acetophenone mediated by samarium diiodide to give both enantiomers of the optically active γ-butyrolactone was described. The best enantiomeric excess of the products was 60%.

Samarium(II) Diiodide Induced Polarity Inversion of π-Allyl Palladium Complexes: The Formation of Allylic Selenides

Allylic acetates were reduced with Pd(0)-SmI2 in the presence of ArSeBr to form corresponding allylic selenides in good yields.

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

Phenylthiotrimethylsilane is reduced hy samarium diiodide to yield samarium phenylthiolate. This new thiolate anion species reacts with acyl chlorides mildly to give thiolesters in good yields.

Crystal Structure of 4, 5-trans-2-Amino-1, 3, 3-tricyano-4, 5-di (4-chlorophenyl)cyclopentene. Ethanol. Monohydrate

The crystal and molecular structure of 4, 5-trans-2-amino-1, 3, 3-tri-cyano-4, 5-di(4-chlorophenyl) cyclopentene. ethanol - monohydrate has been deter-mined by X-ray diffraction method. The crystal (C20H12N4Cl2. C2H6O. H2O, Mr=443. 33) is triclinic with space group P1, a= 11. 033(4), b= 12. 199(3), c= 10. 732(3) A, a=114. 46(2), β=118. 33(3) γ=81. 56(3), V=1155- 1(7) A3, Z=2, Dc= 1. 275g/cm3, μ(MoKa) = 3. 05cm-1, F(000) = 460, R= 0. 070, Rw = 0. 089 for1965 observed reflections (I>3(I)). The phenyl groups are in equatorial positionsand form dihedral angles of 67. 89 and 63. 77° with the central 5-ring. X-ray analysisreveals that in the five membered ring the C (1) -C (2) bond is longer than normal double C=C bond while the C(2) -N (2) bond is shorter than normal C(sp)2-N bond.

Crystal Structure of 3, 4-trans-4, 5-trans-2-Amino-3-cyano-1, 3-diethyloxy carbonyl- 4, 5-di (4-chlorophenyl)cyclopentene

The crystal and molecular structure of 3,4-trans-4, 5-trans-2-amino-3cyano-1, 3-diethyloxy carbonyl-4, 5-di (4-chlorophenyl ) cyclopentene has been determined by X-ray diffraction method. The crystal (C24H22O4N2Cl2, Mr = 473. 35) ismonoclinic with space group P21/c, a= 6. 923(1), b= 33. 178(5), c= 10. 644 (3)β=99. 86(2)°, V=2408. 8(8) A3, Z= 4, Dc= 1. 305g/cm3,μ(MoKa) = 3. 01cm-1,F(000) =984, R=0. 052, Rw=0. 067 for 2147 observed reflections (I>3(I)). Thephenyl groups and the alkoxy carbonyl group are in equatorial positions. The phenylgroups form dihedral angles bf 70. 67 and 66. 74° with the central five-membered ring.

Radical reduction of Passerini 3CR adducts by SmI_2/HMPA

The Passerini 3-CR adducts of substituted cinnamaldehydes,isocyanides and acetic acid were treated with SmI2/HMPA in dry tetrahydrofuran（THF） at room temperature,andβ,γ-unsaturated amides were obtained in moderate yields.The reaction was supposed involving a radical reduction procedure.

SmI_2-promoted imino-Reformatsky reaction for facile synthesis of enantioenriched β-amino acid esters

A facile and efficient method for the stereoselective synthesis of β-amino acid esters via SmI2-promoted imino-Reformatsky reaction is described.Asymmetric addition of tert-butyl bromoacetate to N-tert-butanesulfinyl aldimines afforded β-amino acid esters in moderate to high yields with excellent diastereoselectivities.The synthetic utilities of the tert-butyl β-amino acid esters were expanded by the preparation of β-lactams and 3-aminoindan-1-ones derivatives.

Synthesis of the Cyclopentenylamine Derivatives Promoted by SmI_2

The intermolecular reductive coupling of 1,1-diaryl-2,2-dicya-noethylenes with cinnamic esters promoted by samarium(II) iodide was studied. Functionalized cyclopentenylamine derivatives were prepared in good yields under neutral and mild conditions.

A New Synthetic Method of Highly Substituted Cyclopentadienes from α,β-Unsaturated Alkynones

Promoted by samarium diiodide in THF, the α,β-unsaturated alkynones were reduced to afford intermolecular reductive coupling products. The multiply substituted cyclopentadienes were prepared conveniently in good yields.