118319-39-4

Upstream product

• 13329-40-3 4-Iodoacetophenone 
• 118319-34-9 (E)-1-(dimethylfluorosilyl)-1-octene 
• 201230-82-2 carbon monoxide 
• 118319-47-4 difluoro(methyl)[(E)-1-octenyl]silane 
• 99-90-1 para-bromoacetophenone 
• 111-66-0 oct-1-ene 
• 853955-61-0 (E)-[2-(hydroxymethyl)phenyl]-dimethyl-(1-octenyl)-silane 
• 99-91-2 para-chloroacetophenone 
• 134837-65-3 1-octenyltriethoxysilane 
• 125378-27-0 (E)-1-(Methyldichlorosilyl)-1-octene 
• 42599-16-6 (E)-1-octen-1-ylboronic acid 

Relevant academic research and scientific papers

A molecular Pd(ii) complex incorporated into a MOF as a highly active single-site heterogeneous catalyst for C-Cl bond activation

The organic palladium complex Pd(H2bpydc)Cl2 (H 2bpydc = 2,2′-bipyridine-5,5′-dicarboxylic acid) was immobilized on a porous metal-organic framework UiO-67 (Zr6O 4(OH)4(bpdc)6, bpdc = para- biphenyldicarboxylate) using a direct incorporation strategy. The use of a large amount of the H2bpdc ligand (90 mol% of the mixed ligands) that can't chelate the Pd complex allowed the formation of isolated Pd single active sites uniformly distributed in the MOF network. Pd(ii) doped UiO-67 is isostructural to the parent UiO-67 framework, with a high surface area and pore volume of ca. 2000 m2 g-1 and 0.79 cm3 g -1, respectively. The material was highly efficient in the catalytic conversion of aryl chlorides, showing remarkably higher activity than the homogeneous Pd counterparts. High yields were achieved in Heck and Suzuki-Miyaura coupling reactions of chloroarenes bearing a wide range of substituents. Moreover, the catalyst was recoverable and reusable, giving essentially identical activity after at least 5 cycles. The combination of the advantages of both homogeneous molecular Pd catalysts and solid MOF structures in this system may bring new opportunity in the development of highly active heterogeneous palladium catalysts for a variety of Pd-catalyzed transformations. This journal is the Partner Organisations 2014.

Silicon-Based Cross-Coupling Reagent and Production Method of Organic Compound Using the Same

In one embodiment of the present invention, a silicon-based cross-coupling reagent is disclosed which is a highly stable tetraorganosilicon compound allowing for a cross-coupling reaction under mild reaction conditions without using fluoride ions, transition metal promoter, or strong bases, and the residue of the silicon reagent can be recovered and reused. The silicon-based cross-coupling reagent is a silicon compound in which an o-hydroxymethylphenyl group is connected to a silicon atom for intramolecular activation.

Aqueous sodium hydroxide promoted cross-coupling reactions of alkenyltrialkoxysilanes under ligand-free conditions

(Chemical Equation Presented) Fluoride-free cross-coupling reactions of alkenyltrialkoxysilanes with aryl iodides, bromides, and chlorides are performed on water using sodium hydroxide as activator at 120 °C under normal or microwave heating. This process occurs in the presence of Pd(OAc)2 or 4-hydroxyacetophenone oxime-derived palladacycle 1 as precatalysts under ligand-free conditions with low Pd loadings (0.01-1 mol %) and using tetra-n-butylammonium bromide as additive. Different commercially available vinylalkoxylsilanes can be cross-coupled under these reaction conditions to the corresponding styrenes, the best substrates being vinyltrimethoxy- or vinyltriethoxysilane. Alkenyltriethoxysilanes, prepared by Wilkinson-catalyzed hydrosilylation of alkynes with triethoxysilane, are stereospecifically arylated with aryl and vinyl halides under microwave irradiation in moderate to high β/α regioselectivity affording unsymmetrical stilbenes, alkenylbenzenes, and conjugate dienes, respectively. This simple procedure allows the palladium recycling from the aqueous phase during three runs by extractive separation of the products, which contain very low levels of Pd (21-27.5 ppm for an aryl iodide and up to 76 ppm for a bromide).

Palladium-tetraphosphine catalysed heck reaction with simple alkenes: Influence of reaction conditions on the migration of the double bond

The Heck reaction of aryl halides with simple alk-1-enes is a powerful method for the synthesis of (E)-1-arylalk-1-ene derivatives. The major problem of this reaction is the palladium-catalysed migration of the carbon-carbon double bond along the alkyl ch

Synthesis and cross-coupling reaction of alkenyl[(2-hydroxymethyl)phenyl]dimethylsilanes

Highly stable alkenyl[2-(hydroxymethyl)phenyl]dimethylsilanes are prepared by stereo- and regioselective hydrosilylation of alkynes catalyzed either by a platinum or ruthenium catalyst using protected [2-(hydroxymethyl)phenyl]dimethylsilanes. Cyclic silyl ether, 1,1-dimethyl-2-oxa-1-silaindan, also serves as a starting material for the alkenylsilanes by the ring-opening reaction with alkenyl Grignard reagents. The resulting alkenylsilanes undergo cross-coupling reaction with various aryl and alkenyl iodides under reaction conditions employing K2CO3 as a base at 35-50 °C in highly regio- and stereospecific manners. The reaction tolerates a diverse range of functional groups including silyl protections. The silicon residue is readily recovered and reused on a gram-scale synthesis. Intramolecular coordination of a proximal hydroxyl group is considered to efficiently form pentacoordinate silicates having a transferable group possibly at an axial position and, thus, responsible for the cross-coupling reaction under conditions significantly milder than those reported for the silicon-based reactions.

Alkenyl- and aryl[2-(hydroxymethyl)phenyl]dimethylsilanes: An entry to tetraorganosilicon reagents for the silicon-based cross-coupling reaction

Alkenyl- and aryl[2-(hydroxymethyl)phenyl]dimethylsilanes, highly stable tetraorganosilicon reagents, are found to react with aryl and alkenyl iodides in the presence of a palladium catalyst and K2CO3 as a base, significantly milder conditions compared with those ever reported for the silicon-based cross-coupling reactions. The reaction tolerates a wide range of functional groups, including silyl protectors, and allows a gram-scale synthesis to recover and reuse the silicon residue. Copyright

Heck reaction of aryl halides with linear or cyclic alkenes catalysed by a tetraphosphine/palladium catalyst

cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C 3H5)]2 system catalyses efficiently the Heck reaction of aryl halides with linear alkenes such as pent-1-ene, oct-1-ene or dec-1-ene. Selectivities up to 70% in favour of E-1-arylalk-1-ene isomers can be obtained. In the presence of cyclic alkenes the selectivities of the reactions strongly depends on the ring size. Addition to cyclohexene or cycloheptene led mainly to 1-arylcycloalk-3-ene derivatives. On the other hand, addition to cyclooctene led to 1-arylcycloalk-1-ene adducts.

Synthesis and cross-coupling reactions of tetraalkylammonium organotrifluoroborate salts

Treatment of organoboronic acids with hydrofluoric acid generates an in situ tetracoordinate hydronium organotrifluoroborate species which undergoes counterion exchange with tetra-n-butylammonium hydroxide. The resultant tetraalkylammonium salts are as air and moisture stable as their potassium organotrifluoroborate counterparts with the added advantage of being readily soluble in organic media. They were found to undergo Pd-catalyzed Suzuki-Miyaura cross-couplings with a variety of aryl- and alkenylhalides under mild conditions. Their Pd-catalyzed cross-coupling with acid halides is also possible for the generation of ketones.

CARBONYLATIVE COUPLING REACTION OF ORGANOFLUOROSILANES WITH ORGANIC HALIDES PROMOTED BY FLUORIDE ION AND PALLADIUM CATALYST

Palladium-catalyzed carbonylative cross coupling reaction of organofluorosilanes with organic halides was achieved in the presence of fluoride ion and an atmospheric pressure of carbon monoxide.Alkenyl- or arylfluorosilanes effectively underwent this reaction with alkenyl or aryl iodides in moderate to good yields.Thus, highly functionalized ketones are readily available without protection of reactive functional group such as aldehyde, ketone, ester, nitril, and alcohol.For smooth ketone formation, use of organofluorosilanes is essential; tetraorganosilanes like aryl(trimethyl)silanes, upon reaction with aryl iodides, gave aroyl fluorides instead. Key Words: carbonylative coupling; organofluorosilanes; ketone synthesis

Alkenylfluorosilanes as Widely Applicable Substrates for the Palladium-Catalyzed Coupling of Alkenylsilane/F- Reagents with Alkenyl Iodides

Introduction of fluorine(s) to the silyl groups of alkenylsilanes accelerated the rate of the coupling reaction with alkenyl iodides mediated by fluoride ion and palladium catalyst.The new version of the silicon-based coupling reaction has provided a general and highly stereospecific route to 1,3-dienes as well as alkenylarenes.