Synthesis of Enamines via the Cross-coupling of Thioamides and Diarylketones Promoted by the Sm/SmI_(2)Mixed Reagent

Enamines, promoted by the samarium/samarium diiodide mixed reagent, were synthesized via the cross-coupling of thioamides and diarylketones in good yields.

Immobilization of metal-organic molecular cage on g-C3N4 semiconductor for enhancement of photocatalytic H2 generation

A new compound based on immobilizing of Pd6(RuL3)8(BF4)28 (L=2-(pyridin-3-yl)-1H-imidazo [4,5-f][1,10]-phenanthroline) cage (MOC-16) on g-C3N4 was synthesized. Infrared spectrum and powder X-ray diffraction were used to characterize structure of hybrid MOC-16/g-C3N4, as well as UV-vis absorption spectrum and X-ray photoelectron spectroscopy were carried out to unveil photocatalytic mechanism. With the introduction of MOC-16, the absorption edge of MOC-16/g-C3N4 in UV-vis spectrum extended apparently to long-wavelength region compared with pristine g-C3N4. H2 evolution yielded with MOC-16/g-C3N4 in aqueous solution containing TEOA was much higher than that with RuL3/g-C3N4, Pd/RuL3/g-C3N4 and mixture of MOC-16 and g-C3N4, showing that the octahedral cage structure with high-efficient electron transfer and the interface interaction between MOC-16 and g-C3N4 were significant for improvement of H2 evolution.

Pd-catalyzed sequential reaction for the synthesis of fused tricyclic compounds containing a dihydrofuran or isobenzofuranone unit

A novel Pd-catalyzed sequential reaction for the synthesis of fused tricyclic compounds with a dihydrofuran or isobenzofuranone unit was developed.

Addition of Allyltrimethylsilane to tert-Butanesulfinyl Imines Triggered by Tetra-n-butylammonium Fluoride

The addition of allyltrimethylsilane to tert-butanesulfinyl imines triggered by tetra-n-butylammonium fluoride （TBAF） in the presence of 4A molecular sieves has been studied, and homoallylsulfinamides were obtained in good yields with moderate to high diastereoselectivities.

Facile and Stereoselective Synthesis of N-Substituted Benzotriazole with Baylis-Hillman Adducts

A convenient method has been developed toward the stereoselective synthesis of N-substituted benzotriazole derivatives under mild conditions. The good stereolectivity, high yields and the simple procedure make the present protocol attractive.

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.

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.

Study on the reactions of azo compounds with acyl halides mediated by Sm/TiCl_4

Amides can be obtained in good to excellent yield by Sm/TiCl4 mediated reductive cleavage of N=N bond in azo compounds and successive acylation in one pot. It offers an alternative method for the synthesis of amides from very simple starting materials directly.

SYNTHESES OF TETRAHEDRAL METAL CLUSTER COMPOUNDS

The carbyne compound [Br(CO)_2(Py)_2Mo(≡CC_6H_5)] (Py=pyridine) (1a) reacts with Co_2 (CO)_8, Fe_2(CO)_9 and Mn_2 (CO)_(10) to give tetrahedral tri-metal cluster compounds Co_2Mo(μ_3-CC_6H_5)Br(CO)_8(Py)_2 (2), Fe_2Mo(μ_3-CC_6H_5) Br(CO)_9(Py)_2 (3) and Mn_2Mo(μ_3-CC_6H_5)Br(CO)_(10) (Py)_2 (4) respectively. Tri-metal cluster compound Co_2Mo(μ_3-CC_6H_5)Br(CO)_8-(bipy) (bipy=α,α'dipyridyl) (5) is prepared in a similar reaction sequence from [Br(CO)_2(bipy)Mo(≡CC_6H_5)] (1b) and Co_2(CO)_8. IR, ~1H and ^(13)C NMR spectral data of these compounds are reported and discussed. The crystal structure of compound (5) has been determined by X-ray diffraction.

Studies on K2CO3-Catalyzed 1,4-Addition of 1,2-Allenic Ketones with Diethyl Malonate: Controlled Selective Synthesis of β, γ-Unsaturated Enones and α-Pyrones

The reaction of diethyl malonate with various substituted 1,2-allenic ketone can be catalyzed by 10% of K2CO3leading to polyfunctionalized β, γ-unsaturated enones 3 or 4. With 3-unsaturated 1-substituted-1, 2-allenic ketones, the highly selective formation of β, γ-unsaturated enones 4 was observed; with 1,2-allenic ketones with one or two γ-substituents, only β, γ-unsaturated enones 3 with an unmigrated carbon-carbon double bond were produced; with γ-monosubstituted-1,2-allenic ketones the corresponding (E)-3 were formed highly selectively; with propadienyl ketones, a mixture of β, γ-unsaturated enones 3 and 4 were formed.……

Mono-Allylation of Gem-Diacetates with Allylsamarium Bromide

The substitution reaction between gem-diacetates and allylsamarium bromide was investigated, and homoallylic alcohol acetates were obtained in moderate to good yields.

Cu(Ⅰ)-catalyzed cascade reaction of N-tosylhydrazones with 3-butyn-1-ol:A new synthesis of tetrahydrofurans

The Cu(I)‐catalyzed cascade coupling/cyclization reaction of N‐tosylhydrazones with 3‐butyn‐1‐ol has been explored. This new strategy represents a simple platform for the synthesis of tetrahydrofurans in moderate to good yields.

Regio- and stereo-selective synthesis of multi-substituted 3-pyrrolines

A regio- and stereo-selective synthesis of multi-substituted 3-pyrrolines has been developed. The multi-substituted 3-pyrrolines were synthesized in good yields by 1,3-dipolar cycloaddition of methyl 2-（phenylselanyl）acrylate with azomethine ylides, followed by N-acylation and oxidation-elimination of phenylseleno group. 2009 Xian Huang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

The facile insertion of β-keto sulfones to arynes:The direct preparation of polysubstituted ortho-keto benzyl sulfones

One novel carbon-carbon bond insertion reaction of arynes has been developed. By this reaction β-keto sulfones can insert the triple bond of arynes to prepare polysubstituted ortho-keto benzyl sulfones.

WO_(3)/Salan/30%H_(2)O_(2):a Heterogeneous Catalytic System for the Asymmetric Oxidation of Sulfides

The asymmetric oxidation of sulfides catalyzed by WO3 and 30% H2O2 in the presence of salan as chiral ligands under heterogeneous conditions is described. The reaction system is very easily to be operated. Mild to high chemical yields and moderate enantioselectivities were obtained.

Synthesis and Crystal Structure of an Incomplete Cubane-like Heterobimetallic Cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]

The reaction of[（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]1 with Na2S in MeCN produced a trinuclear cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563（3）, b = 8.9547（18）, c = 17.846（4） A, β = 101.29（3）°, V = 2438.9（9） A^3, Z = 4, Dc = 1.878 g/cm^3, T = 193（2） K, C20H30ClCuMo2S4, Mr = 689.60, F（000） = 1376, μ（MoKa） = 2.335 mm ^-1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I 〉 20-（I）. In the structure of 2, one [（η^5-C5Me5）2Mo2（μ-S）2S] moiety and one CuCI unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one ,μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519（7） and 2.7689（8） A, respectively.

Selective Deoxygenation of Nitrones Mediated by Sm/CoCl_26H_2O Reductive System

In the presence of metallic samariumcobalt (II) chloride hexahydrate, the nitrones can be reduced to the corresponding imines in moderate to high yields under mild and neutral conditions.

Free radical mediated bromization of methylenecyclopropanes: Preparation of 2,4-dibromobutenes without transition metal

A series of 2,4-dibromobutenes were synthesized by the reaction of methylenecyclopropanes with KBr in HOAc in the presence of dibenzoyl peroxide, providing an environment friendly method for the synthesis of 2,4-dibromobutenes.

Crystal Structure of (E,E)-1,10-Bis-(4-fluoro-phenyl)-3,8-dimethyl-deca-3,7-diene-1,10-dione

The crystal and molecular structures of (E,E)-1,10-bis-(4-fluorophenyl)-3,8-dime- thyl-deca-3,7-diene-1,10-dione have been determined by X-ray diffraction method. The crystal (C24- H24F2O2, Mr = 382.45) is of monoclinic, space group P21/c, a = 11.0392(5), b = 11.3620(4), c = 7.9361(3) ?, β = 97.423(2)o, V = 987.06(7) ?3, Z = 2, Dc = 1.287 g/cm3, μ(Mo-Kα) = 0.93 cm-1, λ = 0.7107 ?, F(000) = 404.00, the final R = 0.0530 and wR = 0.150 for 1348 observed reflections (I > 2σ(I)). X-ray analysis revealed that there exists a double bond in C(9)–C(11) with the bond length of 1.324(3) ?, while the C(8)–C(9) bond length is 1.508(3) ? and it may be assigned to a single bond. These results show that the C=C bond is not conjugated with the C=O bond.

Synthesis and Crystal Structure of {η~5:η~1-[(2-Methoxyphenyl)-isopropyl]-indenyl}(dimethoxyethylene)lithium1

The title compound {η^5：η^1-[（2-MeOC6H4）C3H6]CgH6}Li（DME） （DME=1,2-dimethoxy-ethylene） was synthesized by the treatment of 3-[（2-methoxyphenyl）-isopropyl]-indene with 1 equiv, of n-BuLi followed by the recrystallization from a mixed solution of toluene and DME. The compound crystallizes in orthorhombic system, pace group Pbca with a=14.5677（3）, b=15.54670（10）, c=18.7498（3）A°, Z=8, V=4246.45（11）A°^3, Dc=1.127 g/cm^3 and μ（MoKα）=0.072 mm^-1. The coordination geometry can be described as a distorted tetrahedron.