80254-87-1

Upstream product

• 459-45-0 4-fluorobenzenediazonium tetrafluoroborate 
• 1126-46-1 Methyl 4-chlorobenzoate 
• 1194-02-1 4-fluorobenzonitrile 
• 99768-12-4 4-methoxycarbonylphenylboronic acid 
• 4363-35-3 Dihydroxy-styryl-boran 

Downstream Products

• 644-08-6 4-Methylbiphenyl 
• 147497-56-1 (4'-Fluoro-biphenyl-4-yl)-methanol 
• 5731-10-2 4'-fluoro-biphenyl-4-carboxylic acid 

Relevant academic research and scientific papers

A Radical Chain: Mononuclear “Gold Only” Photocatalysis

We herein report an unprecedented reactivity of mononuclear gold catalysts acting as classical catalysts and at the same time as active partners in a radical chain mechanism, whereby gold is the only catalyst. The mechanism of the photo-induced photosensitizer-free “gold only”-catalyzed cross coupling was studied in detail – experimentally and theoretically – based on the reaction between arylboronic acids and aryldiazonium salts. With a systematic set of stoichiometric experiments under various conditions and analytic methods, we could show that this mechanism is initiated by an aryl radical formed in the presence of blue LEDs and MeOH. This aryl radical enters the catalytic cycle to oxidize gold(I) to gold(II). Single electron transfer from gold(II) to the aryldiazonium salt then gives the cationic gold(III) complex by formation of a chain-supporting aryl radical which then is enabled to start a new cycle by oxidation of gold(I) without the need for irradiation. At least every 432 cycles of the radical chain, a new chain-initiating radical has to restart the radical chain. Eventually, the boronic acid is activated by the BF4? anion to transmetalate to gold(III), and reductive elimination delivers the desired product.

Cobalt-catalyzed C(sp2)?CN bond activation: Cross-electrophile coupling for biaryl formation and mechanistic insight

Herein, we report a cross-electrophile coupling of benzonitrile derivatives and aryl halides with a simple cobalt-based catalytic system under mild conditions to form biaryl compounds. Even though the cobalt catalyst is able to activate the C(sp2)?CN bond alone, the use of the AlMe3 Lewis acid enhances the reactivity of benzonitriles and improves the cross-selectivity with barely any influence on the functional group compatibility. X-ray structure determination of an original low-valent cobalt species combined with catalytic and stoichiometric reactions reveals a catalytically active cobalt(I) species toward the aryl halide partner. On the other hand, experimental insights, including cyclic voltammetry experiments, suggest the involvement of a cobalt complex of a lower oxidation state to activate the benzonitrile derivative. Finally, density functional theory calculations support the proposed mechanistic cycle involving two low-valent cobalt species of different oxidation states to perform the reaction.

para-Selective arylation and alkenylation of monosubstituted arenes using thianthreneS-oxide as a transient mediator

Using thianthreneS-oxide (TTSO) as a transient mediator,para-arylation and alkenylation of mono-substituted arenes have been demonstratedviaapara-selective thianthrenation/Pd-catalyzed thio-Suzuki-Miyaura coupling sequence under mild conditions. This reaction features a broad substrate scope, and functional group and heterocycle tolerance. The versatility of this approach was further demonstrated by late-stage functionalization of complex bioactive scaffolds, and direct synthesis of some pharmaceuticals, including Tetriprofen, Ibuprofen, Bifonazole, and LJ570.

Preparation method of para-substituted aryl compound

The invention discloses a preparation method of a para-substituted aryl compound shown as a formula (I) which is described in the specfication. The preparation method is characterized by comprising the following step of: subjecting an aryl sulfonium salt shown as a formula (II) which is described in the specfication and boride to a coupling reaction in a solvent in an inert atmosphere under the action of alkali and a palladium catalyst to obtain the para-substituted aryl compound. According to the method, mono-substituted aromatic hydrocarbon is taken as a substrate, the aryl sulfonium salt isconstructed in situ, and the palladium catalyst catalyzes the aryl sulfonium salt constructed in situ to undergo the Suzuki-Miyaura coupling reaction, so a mono-substituted aromatic hydrocarbon para-arylation or alkenylation product is constructed quickly and efficiently. The method is mild in conditions, high in substrate universality and wide in tolerance of a heterocyclic coupling substrate.

N-acylsulfonamide apoptosis promoters

N-Benzoyl arylsulfonamides having the formula are BCL-Xl inhibitors and are useful for promoting apoptosis. Also disclosed are BCL-Xl inhibiting compositions and methods of promoting apoptosis in a mammal.