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Upstream product

• 766-85-8 3-methoxy-1-iodobenzene 
• 1094752-93-8 methyl 3-(N-methylsulfamoyl)benzoate 
• 63555-50-0 methyl 3-chlorosulfonylbenzoate 
• 618-91-7 methyl 3-iodo-benzoate 
• 65-85-0 benzoic acid 
• 10365-98-7 3-methoxyphenylboronic acid 
• 618-51-9 3-Iodobenzoic acid 
• 53392-03-3 (3-methoxyphenyl)triethoxysilane 
• 186581-53-3 diazomethane 
• 53392-02-2 trichloro(3-methoxyphenyl)silane 
• 2905-65-9 methyl 3-chlorobenzoate 
• 50625-29-1 3-methoxybenzenetrifluorosilane 

Relevant academic research and scientific papers

Bimetallic Cooperative Catalysis for Decarbonylative Heteroarylation of Carboxylic Acids via C-O/C-H Coupling

Cooperative bimetallic catalysis is a fundamental approach in modern synthetic chemistry. We report bimetallic cooperative catalysis for the direct decarbonylative heteroarylation of ubiquitous carboxylic acids via acyl C-O/C-H coupling. This novel catalytic system exploits the cooperative action of a copper catalyst and a palladium catalyst in decarbonylation, which enables highly chemoselective synthesis of important heterobiaryl motifs through the coupling of carboxylic acids with heteroarenes in the absence of prefunctionalization or directing groups. This cooperative decarbonylative method uses common carboxylic acids and shows a remarkably broad substrate scope (>70 examples), including late-stage modification of pharmaceuticals and streamlined synthesis of bioactive agents. Extensive mechanistic and computational studies were conducted to gain insight into the mechanism of the reaction. The key step involves intersection of the two catalytic cycles via transmetallation of the copper–aryl species with the palladium(II) intermediate generated by oxidative addition/decarbonylation.

Reductive Coupling of Aryl Halides via C—H Activation of Indene

This paper describes the first case of a reductive coupling reaction with indene, a non-heteroatom olefin used as a reducing agent. The scope of the substrate is wide. The homo-coupling, cross-coupling, and synthesis of 12 and 14-membered rings were realized. The control experiment, indene-product curve and density functional theory calculations showed that the η3-palladium indene intermediate was formed by C—H activation in the presence of cesium carbonate. We speculate that the final product was obtained through a Pd (IV) intermediate or aryl ligand exchange. In addition, we excluded the formation of palladium anion (Pd(0)?) intermediates.

N-Aroylsulfonamide-Photofragmentation (ASAP)-A Versatile Route to Biaryls

The photochemical fragmentation of N-aroylsulfonamides 9 (ASAP) is a powerful method for the preparation of various biaryls. Compounds 9 are easily accessible in two steps from amines by treatment with arenesulfonyl chlorides and aroyl chlorides. Many of these compounds were prepared for the first time. The irradiation takes place in a previously developed continuous-flow reactor using inexpensive UVB or UVC fluorescent lamps. Isocyanates and sulphur dioxide are formed as the only by-products. The ASAP tolerates a variety of functional groups and is even suited for the preparation of phenylnaphthalenes and terphenyls. The ASAP mechanism was elucidated by interaction of photophysical and quantum chemical (DFT) methods and revealed a spirocyclic biradical as key intermediate.

Very efficient and broad-in-scope palladium-catalyzed Hiyama cross-coupling. the role of water and copper(I) salts

A very high-yielding Pd-catalyzed cross-coupling between aryl halides and aryl(trialkoxy)silanes is achieved in the presence of Cu(i) and a measured amount of water. This novel methodology is useful for the generation of a wide range of biaryls, particularly non-para substituted derivatives, which are usually less reported.

Palladium-catalyzed cross-coupling reactions of arylsiloxanes with aryl halides: Application to solid-supported organic synthesis

The solid-phase version of the Pd-catalyzed Hiyama reaction between a variety of aryltriethoxysilanes and immobilized aryl halides was developed. Smooth cross-coupling was achieved to afford the corresponding biaryl products in moderate to excellent yields. The described protocol would be particularly useful for the construction of 4′-substituted 1,1′-biphenyl derivatives.

Palladium-catalyzed Hiyama cross-coupling of aryltrifluorosilanes with aryl and heteroaryl chlorides

An efficient, palladium-catalyzed Hiyama cross-coupling reaction of aryltrifluorosilanes with aryl chlorides has been developed. A wide variety of functionalized biaryl derivatives were isolated in good to excellent yields. The scope of this reaction has also been extended to heteroaryl chlorides, affording the corresponding heterobiaryl compounds in high yields.