Copper(I) chloride-mediated oxidative coupling of alkenyltrialkylstannyl functions: efficient stereocontrolled syntheses of uniquely functionalized conjugated diene systems

1997 ◽  
Vol 75 (6) ◽  
pp. 694-701 ◽  
Author(s):  
Edward Piers ◽  
Ernest J. McEachern ◽  
Miguel A. Romero ◽  
Patricia L. Gladstone
Keyword(s):  
Oxidative Coupling ◽  
Room Temperature ◽  
Conjugated Dienes ◽  
Conjugated Diene ◽  
Copper Metal ◽  
Unsaturated Esters

Treatment of the β-trialkylstannyl α,β-unsaturated esters 1–9 with 2.5 equivalents of copper(I) chloride in N,N-dimethylformamide at room temperature results in the efficient, stereocontrolled production of the highly functionalized conjugated dienes 10–18, respectively. In each of these oxidative couplings, production of 1 equivalent of product is accompanied by the formation of 2 equivalents of both the trialkylstannyl chloride and copper metal. Keywords: alkenyltrialkylstannanes, copper(I) chloride, transmetalation, conjugated dienes, oxidative coupling, β-trialkylstannyl α,β-unsaturated esters, substituted dialkyl muconates, organostannane, organocopper.

scholarly journals Synthesis of 1,1′-Bis(1-Methyl/Chloro-2,3,4,5-Tetraphenyl-1-Silacyclopentadienyl) [Ph4C4Si(Me/Cl)-(Me/Cl)SiC4Ph4] from Silole Anion [MeSiC4Ph4]−•[Li+ or Na+] and Silole Dianion [SiC4Ph4]2−•2[Li+]; Oxidative Coupling of Silole Anion [MeSiC4Ph4]−•[Li+ or Na+] by Ferrous Chloride (FeCl2) and Oxidative Coupling and Chlorination of Silole Dianion [SiC4Ph4]2−•2[Li+] by Cupric Chloride (CuCl2)

Molecules ◽  
2019 ◽  
Vol 24 (20) ◽  
pp. 3772
Author(s):  
Hong
Keyword(s):  
Oxidative Coupling ◽  
Room Temperature ◽  
Cupric Chloride ◽  
High Yield ◽  
Cuprous Chloride ◽  
Ferrous Chloride ◽  
Copper Metal ◽  
Iron Metal ◽  
Chloride Salts ◽  
Solution Changes

A reaction of silole anion {[MeSiC4Ph4]−•[Li+ or Na+] (1) with anhydrous ferrous chloride (FeCl2) in THF (tetrahydrofuran) gives 1,1′-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl) [Ph4C4Si(Me)-(Me)SiC4Ph4] (2) with precipitation of iron metal in high yield. Silole dianion {[SiC4Ph4]2−•2[Li+] (3) is added to anhydrous cupric chloride (CuCl2) in THF at −78 °C, then the dark red solution changes into a greenish solution. From the solution, a green solid is isolated, and stirring it in toluene at room temperature provides quantitatively 1,1′-bis(1-chloro-2,3,4,5-tetraphenyl-1-silacyclopentadienyl) [Ph4C4Si(Cl)-(Cl)SiC4Ph4] (4) with precipitation of copper metal in toluene. The green solid is suggested to be 1,1′-bissilolyl bisradical [Ph4C4Si-SiC4Ph4]2• (8), and lithium cuprous chloride salts {[Li2CuICl2]+•[CuICl2]−}. Both reactions are initiated by single-electron transfer (SET) from the electron-rich anionic silole substrates (1 and 3) to iron(II) and copper(II).

Room temperature selective oxidation of aniline to azoxybenzene over a silver supported tungsten oxide nanostructured catalyst

2015 ◽  
Vol 17 (3) ◽  
pp. 1867-1876 ◽  
Author(s):  
Shilpi Ghosh ◽  
Shankha S. Acharyya ◽  
Takehiko Sasaki ◽  
Rajaram Bal
Keyword(s):  
Silver Nanoparticles ◽  
Tungsten Oxide ◽  
Selective Oxidation ◽  
Oxidative Coupling ◽  
Room Temperature ◽  
Heterogeneous Catalysts ◽  
Nanostructured Catalyst ◽  
Important Chemical

Heterogeneous catalysts comprising silver nanoparticles supported on nanostructured tungsten oxide were applied for room temperature oxidative coupling of aniline to azoxybenzene, an important chemical intermediate and a chemical of industrial interest.

ChemInform Abstract: Facile Synthesis of Dibranched Conjugated Dienes via Palladium-Catalyzed Oxidative Coupling of N-Tosylhydrazones.

ChemInform ◽  
2014 ◽  
Vol 45 (5) ◽  
pp. no-no
Author(s):  
Huanfeng Jiang ◽  
Li He ◽  
Xianwei Li ◽  
Huoji Chen ◽  
Wanqing Wu ◽  
...  
Keyword(s):  
Oxidative Coupling ◽  
Conjugated Dienes ◽  
Facile Synthesis ◽  
Palladium Catalyzed

CuWO4 as a photocatalyst for room temperature aerobic benzylamine oxidation

2018 ◽  
Vol 54 (9) ◽  
pp. 1101-1104 ◽  
Author(s):  
Aaron D. Proctor ◽  
Shobhana Panuganti ◽  
Bart M. Bartlett
Keyword(s):  
Oxidative Coupling ◽  
Oxidation Reaction ◽  
Room Temperature ◽  
Photo Oxidation

We report the first example of a controlled photo-oxidation reaction on CuWO4, the aerobic oxidative coupling of benzylamine.

Hydroformylation of unsaturated esters and 2,3-dihydrofuran under solventless conditions at room temperature catalysed by rhodium N-pyrrolyl phosphine catalysts

2019 ◽  
Vol 43 (43) ◽  
pp. 16990-16999 ◽  
Author(s):  
W. Alsalahi ◽  
A. M. Trzeciak
Keyword(s):  
Vinyl Acetate ◽  
Methyl Acrylate ◽  
Butyl Acrylate ◽  
Room Temperature ◽  
Allyl Acetate ◽  
Unsaturated Esters

Complexes of the type HRh(CO)L3 (where L is an N-pyrrolyl phosphine, e.g. P(NC4H4)3, Ph(NC4H4)2, or PPh2(NC4H4)) were applied in the hydroformylation of less reactive unsaturated substrates (allyl acetate, butyl acrylate, methyl acrylate, 2,3-dihydrofuran, vinyl acetate).

scholarly journals Inhibition by heparin of Fe(II)-catalysed free-radical peroxidation of linolenic acid

1992 ◽  
Vol 286 (3) ◽  
pp. 717-720 ◽  
Author(s):  
M A Ross ◽  
W F Long ◽  
F B Williamson
Keyword(s):  
Linolenic Acid ◽  
Thiobarbituric Acid ◽  
Conjugated Dienes ◽  
Dependent Manner ◽  
Gamma Linolenic Acid ◽  
Conjugated Diene ◽  
Concentration Dependent Manner ◽  
Repeat Units ◽  
Molar Basis ◽  
Endogenous Antioxidants

Heparin, in a concentration-dependent manner, inhibited the generation of conjugated dienes and thiobarbituric acid-positive substances when incubated with Fe2+ and gamma-linolenic acid. In the conjugated diene assay, other glycosaminoglycans, on a molar basis calculated with respect to their respective hydrated disaccharide repeat units, were less effective than heparin. Heparin which had been re-N-sulphonated after removal of both N-sulphonates and O-sulphates, and heparin in which iduronate residues had been reduced to idose residues, were largely unaffected in their activity. Removal of both N-sulphonates and O-sulphates greatly reduced the effectiveness of the heparin. Analysis of the effects of heparin fragments generated by heparinase I treatment of heparin showed that depolymerization decreased the effectiveness of the heparin. It is possible that heparins and related strongly acidic polysaccharides may function as endogenous antioxidants, and that sequestration by them, or harmless oxidation by them, of ions such as Fe2+, contributes to their effectiveness.

Reactions of 7-azaindole with niobium and tantalum pentachlorides and coupling to the azaindolyl-azaindolium cation

1994 ◽  
Vol 72 (7) ◽  
pp. 1675-1683 ◽  
Author(s):  
Jacques Poitras ◽  
André L. Beauchamp
Keyword(s):  
Infrared Spectroscopy ◽  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Infrared Spectra ◽  
Oxidative Coupling ◽  
Room Temperature ◽  
H Nmr ◽  
Counter Ion ◽  
Distorted Octahedral ◽  
Complex Salts

The reaction of NbCl5 and TaCl5 with 7-azaindole (Haza) at room temperature in benzene or dichloromethane yielded MCl5(Haza) addition compounds. Under more severe conditions, the same compound was obtained with TaCl5. For NbCl5, some reduction to Nb(IV) was observed and NbCl5(Haza), NbCl4(Haza)2, and the (H2aza)+ ion were identified in the reaction mixture by infrared spectroscopy. Oxidative coupling of two azaindole units via N7—C6 also took place during the reaction, since the 7-(azaindol-6-yl)azaindolium cation was found as counter-ion in the crystal structures of two complex salts. In the crystals of (H2aza-aza)[NbOCl4(Haza)]•0.5CH2Cl2([Formula: see text]a = 7.255 Å, b = 12.412 Å, c = 14.277 Å, α = 89.03°, β = 85.60°, γ = 76.66°, Z = 2, R = 0.062), the anion is the roughly octahedral [NbOCl4(azaindole)]− species containing a neutral N7-coordinated azaindole trans to the Nb=O bond. The [NbOCl5]2− salt ([Formula: see text]a = 7.527 Å, b = 10.168 Å, c = 10.467 Å, α = 66.41°, β = 84.07°, γ = 85.51°, Z = 1, R = 0.037) contains the distorted octahedral [NbOCl5]2− ion disordered over two orientations. The infrared spectra suggest monomeric octahedral structures for the MCl5(Haza) and NbCl4(Haza)2 complexes. 1H NMR spectroscopy shows that NbCl5(Haza) is not dissociated in CD2Cl2.

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