190065-72-6

Upstream product

• 637-87-6 1-Chloro-4-iodobenzene 
• 629-05-0 n-octyne 
• 106-39-8 bromochlorobenzene 
• 536-74-3 phenylacetylene 
• 201230-82-2 carbon monoxide 
• 33491-03-1 1-(bromoethynyl)-4-chlorobenzene 
• 873-73-4 4-n-chlorophenylacetylene 
• 137595-18-7 1-octynylzinc bromide 

Downstream Products

• 7295-52-5 1-(4-chlorophenyl)-5,5-dimethylhexan-1-one 
• 95110-77-3 1-(4-chlorophenyl)-2-octanone 

Relevant academic research and scientific papers

Binuclear Pd(I)-Pd(I) Catalysis Assisted by Iodide Ligands for Selective Hydroformylation of Alkenes and Alkynes

Since its discovery in 1938, hydroformylation has been thoroughly investigated and broadly applied in industry (>107 metric ton yearly). However, the ability to precisely control its regioselectivity with well-established Rh- or Co-catalysts has thus far proven elusive, thereby limiting access to many synthetically valuable aldehydes. Pd-catalysts represent an appealing alternative, yet their use remains sparse due to undesired side-processes. Here, we report a highly selective and exceptionally active catalyst system that is driven by a novel activation strategy and features a unique Pd(I)-Pd(I) mechanism, involving an iodide-assisted binuclear step to release the product. This method enables β-selective hydroformylation of a large range of alkenes and alkynes, including sensitive starting materials. Its utility is demonstrated in the synthesis of antiobesity drug Rimonabant and anti-HIV agent PNU-32945. In a broader context, the new mechanistic understanding enables the development of other carbonylation reactions of high importance to chemical industry.

Synthesis of trisubstituted alkenes by Ni-catalyzed hydroalkylation of internal alkynes with cycloketone oxime esters

A method for Ni-catalyzed hydroalkylation of internal alkynes with cycloketone oxime esters was developed. The reaction has a broad substrate scope. This hydroalkylation shows excellent regio-and stereo-selectivity. This method enables readily available starting materials to be used to access a range of cyano-substituted single-configuration trisubstituted alkenes. These are valuable feedstock chemicals and are widely used in synthetic and medicinal chemistry.

In Situ Generation of Alkynylzinc and Its Subsequent Negishi Reaction in a Flow Reactor

A highly efficient and convenient Negishi cross-coupling reaction has been developed for the synthesis of unsymmetrical alkynes and enynes in a continuous-flow process. The reaction proceeds through an in situ generated alkynylzinc reagent by the reaction of lithium acetylide with zinc halide at room temperature followed by a cross-coupling reaction with aryl or vinyl iodides. The notable features of this work compared to the conventional benchtop method are mild reaction conditions, good to excellent yields, broad functional-group compatibility, short residence time (73 sec) and especially desilylation of TMS group with the residence time of only 10.5 sec.

Nickel Phosphite/Phosphine-Catalyzed C-S Cross-Coupling of Aryl Chlorides and Thiols

A method for the coupling of aryl chlorides and thiophenols using an air-stable nickel(0) catalyst is described. This thioetherification procedure can be effectively applied to a range of electronically diverse aryl/heteroaryl chlorides without more expensive metal catalysts such as palladium, iridium, or ruthenium. This investigation also illustrates both, a variety of thiol coupling partners and, in certain cases, the use of Cs2CO3.

Palladium-free and phosphine-free Sonogashira coupling reaction of aryl halides with terminal alkynes catalyzed by boehmite nanoparticle-anchored Cu(I) diethylenetriamine complex

In this work, a novel diethylenetriamine-functionalized-boehmite nanoparticle-supported Cu(I) catalyst is synthesized. The catalyst prepared is then characterized by FT-IR spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray

Microwave-enhanced cross-coupling reactions involving alkynyltrifluoroborates with aryl bromides

Palladium-catalyzed alkynylation has emerged as one of the most reliable methods for the synthesis of alkynes which are often used in natural product syntheses and material science. An efficient method for coupling alkynyltrifluoroborates with various aryl bromides in the presence of a palladium catalyst has been developed using microwave irradiation. The microwave reactions are rapid and efficient.

Efficient copper-catalyzed sonogashira couplings of aryl halides with terminal alkynes in water

An efficient copper-catalyzed method has been developed for Sonogashira couplings of aryl halides with terminal alkynes in water. The protocol uses inexpensive CuBr as the catalyst, 1,10-phenanthroline as the ligand, tetrabutylammonium bromide (TBAB) as the phase-transfer catalyst, environmentally friendly water as the solvent, and various internal alkynes were synthesized in good to excellent yields. Georg Thieme Verlag Stuttgart - New York.

Cp*Li as a base: application to palladium-catalyzed cross-coupling reaction of aryl-X or alkenyl-X (X=I, Br, OTf, ONf) with terminal acetylenes

The reaction of aryl-X or alkenyl-X (X=I, Br, OTf, ONf) with terminal acetylenes in the presence of a catalytic amount of Pd(OAc)2 provided the alkynylated products in good yields by using Cp*Li (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) as a base.

Palladium(II) chloride and a (dipyridin-2-ylmethyl)amine-derived palladium(II) chloride complex as highly efficient catalysts for the synthesis of alkynes in water or in NMP and of diynes in the absence of reoxidant

The (dipyridin-2-ylmethyl)amine-derived palladium chloride complex 1 and PdCl2 are efficient catalysts for cross-coupling reactions between terminal alkynes and aryl iodides or bromides under modified Sonogashira-Cassar-Heck conditions. The alkynylation can be performed under copper-free conditions in water at reflux or at room temperature under air with pyrrolidine as base and tetra-n-butylammonium bromide (TBAB) as additive, with TONs of up to 7 × 104 and TOFs (h-1) of up to 6666. Terminal alkynes can be arylated in NMP as well under copper- and amine-free conditions at 110°C or room temperature, with tetra-n-butylammonium acetate (TBAA) acting as base with TONs up to 2 × 105 and TOFs (h -1) up to 66 666. In general, complex 1 displays a slightly higher efficiency than PdCl2 as catalyst and maintains the same activity after five consecutive runs. Alternatively, these alkynylation processes can be carried out under microwave heating conditions. The homocoupling of terminal alkynes to the corresponding 1,3-diynes proceeds under phosphane-free conditions with the (dipyridin-2-yrmethyl)amine-derived palladium chloride complex 1 or with PdCl2 as catalysts and with CuI as cocatalyst in NMP with use of either TBAA or pyrrolidine as bases. This Glaser-type reaction can be performed at 110°C or at room temp. in the presence of air without the use of a reoxidant. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.