79048-32-1

Upstream product

• 636-98-6 p-nitrobenzene iodide 
• 813-19-4 bis(tri-n-butyltin) 
• 100-00-5 4-chlorobenzonitrile 
• 586-78-7 para-nitrophenyl bromide 
• 24850-33-7 allyltributylstanane 
• 688-73-3 tri-n-butyl-tin hydride 

Downstream Products

• 5332-96-7 1-(4-nitrophenyl)propan-2-one 
• 1528-74-1 4,4'-dinitrobiphenyl 
• 846571-47-9 (±)-aureothin 
• 282094-11-5 C₅₆H₅₄O₄NC₆H₄NO₂ 
• 20265-00-3 p-NO₂-C₆H₄HgCl 
• 107624-96-4 3-methoxy-4'-nitro-1,1'-biphenyl 
• 62507-47-5 (3-methoxyphenyl)(4-nitrophenyl)methanone 
• 295356-14-8 (4S,4aR,5S,5aR,6R,12aS)-9-Amino-4-dimethylamino-3,5,10,12,12a-pentahydroxy-6-methyl-8-(4-nitro-phenyl)-1,11-dioxo-1,4,4a,5,5a,6,11,12a-octahydro-naphthacene-2-carboxylic acid amide 

Relevant academic research and scientific papers

Mild and Robust Stille Reactions in Water using Parts Per Million Levels of a Triphenylphosphine-Based Palladacycle

An inexpensive and new triphenylphosphine-based palladacycle has been developed as a pre-catalyst, leading to highly effective Stille cross-coupling reactions in water under mild reaction conditions. Only 500–1000 ppm of Pd suffices for couplings involving a variety of aryl/heteroaryl halides with aryl/hetaryl stannanes. Several drug intermediates can be prepared using this catalyst in aqueous nanoreactors formed by 2 wt % Brij-30 in water.

Stannylation of Aryl Halides, Stille Cross-Coupling, and One-Pot, Two-Step Stannylation/Stille Cross-Coupling Reactions under Solvent-Free Conditions

Solvent-free protocols for palladium-catalyzed stannylation of aryl halides, Stille cross-coupling, and one-pot, two-step stannylation/Stille cross-coupling (SSC) are reported for the first time. (Het)aryl halides bearing acceptor, donor, as well as sterically demanding substituents are stannylated and/or coupled in high yields. The reactions are catalyzed by conventional palladium(II) acetate/PCy3 [Pd(OAc)2/PCy3] under air, using available base CsF, and without the use of high purity reagents. The developed synthetic procedures are versatile, robust, and easily scalable. The absence of solvent, and the elimination of isolation procedures of aryl stannanes makes the SSC protocol simple, step economical, and highly efficient for the synthesis of biaryls in a one-pot two-step procedure.

Layered double hydroxide supported nanopalladium catalyst for Heck-, Suzuki-, Sonogashira-, and Stille-type coupling reactions of chloroarenes

Layered double hydroxide and Merrifield resin supported nanopalladium(0) catalysts are prepared by an exchange of PdCl42- followed by reduction and well characterized for the first time. The ligand-free heterogeneous layered double hydroxide supported nanopalladium (LDH-Pd0) catalyst using the basic LDH in place of basic ligands indeed exhibits higher activity and selectivity in the Heck olefination of electron-poor and electron-rich chloroarenes in nonaqueous ionic liquids (NAIL) over the homogeneous PdCl2 system. Using microwave irradiation, the rate of the Heck olefination reaction is accelerated, manifold with the highest turnover frequency ever recorded in the case of both electron-poor and electron-rich chloroarenes. The basic LDH-Pd0 shows a superior activity over a range of supported catalysts, from acidic to weakly basic Pd/C, Pd/SiO2, Pd/Al2O3, and resin-PdCl42- in the Heck olefination of deactivated electron-rich 4-chloroanisole. The use of LDH-Pd0 is extended to the Suzuki-, Sonogashira-, and Stille-type coupling reactions of chloroarenes in an effort to understand the scope and utility of the reaction. The catalyst is quantitatively recovered from the reaction by a simple filtration and reused for a number of cycles with almost consistent activity in all the coupling reactions. The heterogeneity studies provide an insight into mechanistic aspects of the Heck olefination reaction and evidence that the reaction proceeds on the surface of the nanopalladium particles of the heterogeneous catalyst. TEM images of the fresh and used catalyst indeed show that the nanostructured palladium supported on LDH remains unchanged at the end of the reaction, while the XPS and evolved gas detection by TGA-MS of the used catalyst identify ArPdX species on the heterogeneous surface. Thus, the ligand-free nanopalladium supported on LDH, synthesized by the simple protocol, displays superior activity over the other heterogeneous catalysts inclusive of nanopalladium in the C-C coupling reactions of chloroarenes.

Preparation of Arylbutyltin Having Electron-withdrawing Group by Palladium Catalyzed Reaction of Hexabutylditin with Aryl Iodide

Nitro-, acyl-, and cyanophenyltributyltin can be prepared by the reaction of hexabutylditin with the corresponding aryl iodide in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium.

SYNTHESIS OF ORGANOTRIALKYLSTANNANES. THE REACTION BETWEEN ORGANIC HALIDES AND HEXAALKYLDISTANNANES IN THE PRESENCE OF PALLADIUM COMPLEXES

The aryl halides YC6H4X (X=Br or I) have been shown to react with the distannanes (R3Sn)2 (R=n-Bu or Me) in toluene in the presence of or to give the compounds YC6H4SnR3 for (a) R=n-Bu, Y=H, p-OMe, o-Me, p-Me, m-Cl, p-Cl, m-CN, p-COCH3 and m-NO2, and (b) R=Me, Y=H, p-OMe, p-Me, p-CN, p-COCH3, m-NO2 and p-NO2.Benzyl halides YC6H4CH2X (X=Cl or Br) similarly give YC6H4CH2SnR3 for (a) R=n-Bu, Y=H, m-OMe, p-OMe, m-Cl, m-CN, and m-NO2, and (b) R=Me, Y=m-Cl, m-CN, p-CN and m-NO2.These reactions are of special value as preparative procedures in cases in which Grignard or organolithium reagents cannot be used.Allyl chloride and bromide were likewise shown to react with (n-Bu3Sn)2 to give CH2=CHCH2SnBu3, but n-BuCl and n-BuBr gave only a trace of n-Bu4Sn.The mixed dimetallo species n-Bu3SnSiMe3 was shown to react with aryl bromides YC6H4Br (X=H, p-OMe, p-Me, or p-Cl) to give the arylsilicon compounds YC6H4SiMe3, with no aryltin products.