925459-27-4

Upstream product

• 4466-24-4 2-Butylfuran 
• 100-00-5 4-chlorobenzonitrile 
• 586-78-7 para-nitrophenyl bromide 
• 1415426-04-8 (E)-3-chloro-1-(4-nitrophenyl)oct-2-en-1-one 
• 1038997-90-8 (4-nitrophenyl)(2,4,6-triisopropylphenyl)iodonium triflate 
• 636-98-6 p-nitrobenzene iodide 
• 617-90-3 2-furancarbonitrile 
• 122-04-3 4-nitro-benzoyl chloride 
• 628-71-7 1-Heptyne 

Relevant academic research and scientific papers

A Convoluted Polyvinylpyridine-Palladium Catalyst for Suzuki-Miyaura Coupling and C?H Arylation

The development of highly active and reusable supported catalysts for Suzuki-Miyaura coupling and catalytic C?H arylation is important for fundamental and applied chemistry, with these reactions being used to produce medical compounds and functional materials. Herein, we found that a mesoporous composite made of a linear poly(4-vinylpyridine) and tetrachloropalladate acted as a dual-mode catalyst for a variety of cross-coupling reactions, with both Pd nanoparticles and a Pd complex catalyst being observed under different conditions. The polyvinylpyridine-palladium composite 1 was readily prepared via the molecular convolution of poly(4-vinylpyridine) and sodium tetrachloropalladate to provide a hardly soluble polymer-metal composite. The Suzuki-Miyaura coupling and the C?H arylation of aryl chlorides and bromides with arylboronic acids, thiophenes, furans, benzene, and anisole proceeded in the presence of 0.004 mol% (40 mol ppm) to 1 mol% Pd of 1 to afford the corresponding coupling products in high yields. Furthermore, the catalyst was reused without an appreciable loss of activity. Pharmaceutical compounds and functional materials were synthesized via the coupling reactions. N2 gas adsorption/desorption analysis indicated that the catalyst had a mesoporous nature, which played a crucial role in the catalysis. In the Suzuki-Miyaura couplings, in situ generated palladium nanoparticles in the polymer matrix were catalytically active, while a polymeric Pd(II) complex was crucial in the C?H arylations. These catalytic species were investigated via XAFS, XPS, far-infrared absorption, and Raman spectroscopies, as well as DFT calculations. (Figure presented.).

Benzenesulfonyl chlorides: Alternative coupling partners for regiocontrolled palladium-catalyzed direct desulfitative 5-arylation of furans

The reactivity of furan derivatives in palladium-catalyzed desulfitative arylation was studied. Alkyl-substituted furan derivatives were successfully coupled with a variety of benzenesulfonyl chlorides using a phosphine-free catalyst; regioselective arylation at C5 of the furan was observed in all cases. This reaction tolerates a wide variety of substituents on the benzenesulfonyl derivative. It should be noted that even bromo- and iodobenzenesulfonyl chlorides were successfully coupled with furan derivatives without cleavage of the C-Br or C-I bonds, thus allowing further transformations. The use of these reactants demonstrates the potential of benzenesulfonyl chlorides as coupling partners to access to functionalized 5-arylfurans.

Pd/C as a catalyst for completely regioselective c=h functionalization of thiophenes under mild conditions

The completely C3-selective arylation of thiophenes and benzo[b]thiophenes was achieved by using Pd/C as a heterogeneous catalyst without ligands or additives under mild reaction conditions. The practicability of this transformation is demonstrated by notable functional group tolerance and the insensitivity of the reaction to H2O and air. This method is also applicable to nitrogen- and oxygen-containing heterocycles, yielding the corresponding C2-arylated products. Three-phase tests along with Hg-poisoning and hot-filtration tests suggest that the catalytically active species is heterogeneous in nature. I+ can do better! Pd/C can be used without ligands or additives to catalyze the completely C3-selective arylation of diversely substituted thiophenes and benzo[b]thiophenes under mild reaction conditions. The physical nature of the catalytic species was investigated and the mechanism was studied. Relative rate data generated in a "robustness screen" were used to design a complex substrate that undergoes highly chemoselective sequential functionalization. Copyright

Studies on elimination pathways of β-halovinyl ketones leading to allenyl and propargyl ketones and furans under the action of mild bases

The elimination pathway of stereochemically defined β-halovinyl ketones has been investigated using a mild base, NEt3, leading to the formation of allenyl ketones and propargyl ketones. A preferential α-vinyl enolization of (E)-β-chlorovinyl ke

Congested ferrocenyl polyphosphanes bearing electron-donating or electron-withdrawing phosphanyl groups: Assessment of metallocene conformation from NMR spin couplings and use in palladium-catalyzed chloroarenes activation

The synthesis of novel substituted cyclopentadienyl salts that incorporate both a congested branched alkyl group (tert-butyl, (triphenyl)methyl, or tri(4-tert-butyl)phenylmethyl) and a phosphanyl group is reported. The introduction of either electron-withdrawing or electron-donating substituents (furyl, i-propyl, cyclohexyl, tert-butyl) on P atoms was generally achieved in high yield. The modular synthesis of ferrocenyl polyphosphanes from an assembly of these cyclopentadienyl salts was investigated, leading to the formation of new triphosphanes (denoted as 9-12) and diphosphanes (denoted as 14-16). The resulting phosphanes are not sensitive to air or moisture, even when electron-rich substituents are present. This set of polyphosphanes displays varied conformational features, which are discussed in the light of their multinuclear NMR characterization in solution and of the X-ray solid state structure of the representative triphosphane 1,2-bis(diphenylphosphanyl)- 1′-(diisopropylphosphanyl)-3′-(triphenyl)methyl-4-tert-butyl ferrocene, 11. In particular, the existence of a range of significantly different nonbonded ("through-space", TS) spin-spin coupling constants between heteroannular P atoms, for the triphosphanes of this class, allowed their preferred conformation in solution to be appraised. The study evidences an unanticipated flexibility of the ferrocene platform, despite the presence of very congested tert-butyl and trityl groups. Herein, we show that, contrary to our first belief, the preferred conformation for the backbone of ferrocenyl polyphosphanes can not only depend on the hindrance of the groups decorating the cyclopentadienyl rings but is also a function of the substituents of the phosphanyl groups. The interest of these robust phosphanes as ligands was illustrated in palladium catalysis for the arylation of n-butyl furan with chloroarenes, using direct C-H activation of the heteroaromatic in the presence of low metal/ligand loadings (0.5-1.0 mol %). Thus, 4-chlorobenzonitrile, 4-chloronitrobenzene, 4-chloropropiophenone, and 4-(trifluoromethyl) chlorobenzene were efficiently coupled to n-butyl furan, using Pd(OAc) 2 associated to the new diphosphane ligands 1,1′- bis(diisopropylphosphanyl)-3,3′-di(triphenyl)methyl ferrocene (15) or 1,1′-bis(dicyclohexylphosphanyl)-3,3′-di(triphenyl)methylferrocene (16), which respectively hold the electron-rich -Pi-Pr2 and -PCy 2 groups.

Aversatile palladium/triphosphane system for direct arylation of heteroarenes with chloroarenes at low catalyst loading

Put a ring on it: The use of an air-stable, robust palladium/tridentate phosphane catalyst in direct C-H and C-Cl activation reactions is reported (see scheme; DMAc=N,N-dimethylacetamide, TBAB=tetra-n-butylammonium bromide). Electron-rich, electron-poor, and polysubstituted furans (X=O), thiophenes (X=S), pyrroles (X=NR5), and thiazoles were arylated with chloroarenes in the presence of the catalyst.

N-heterocyclic carbenes: Useful ligands for the palladium-catalysed direct C5 arylation of heteroaromatics with aryl bromides or electron-deficient aryl chlorides

New Pd-N-heterocyclic carbene complexes have been prepared and employed for palladium-catalysed direct arylation of heteroaromatic derivatives by using aryl halides. These catalyst precursors promote the coupling of challenging aryl halides such, as deactivated or congested aryl bromides and also activated aryl chlorides. This procedure employs only 1 mol-% of an air-stable palladium complex. This is a practical advantage over the procedures that employ palladium attached to air-sensitive phosphane ligands, which are often used to promote the coupling of such, aryl halides.

Low catalyst loading ligand-free palladium-catalyzed direct arylation of furans: An economically and environmentally attractive access to 5-arylfurans

The direct 5-arylation of furans at very low catalyst loading using Pd(OAc)2 as catalyst without added ligand proceed in high yields. Turnover numbers up to 10000 have been obtained for the coupling of several activated aryl bromides. A wide ra