13122-30-0

Upstream product

• 67-56-1 methanol 
• 4551-62-6 p-deuterobenzoic acid 
• 619-44-3 methyl 4-iodobenzoate 
• 93524-73-3 5-<(4-methoxycarbonyl)phenoxy>-1-phenyltetrazole 
• 38053-91-7 2-trimethylsilyloxy-1,3-butadiene 
• 922-67-8 propynoic acid methyl ester 
• 619-42-1 4-methoxycarbonylphenyl bromide 
• 28000-56-8 5-(4-carboxyphenoxy)-1-phenyltetrazole 
• 99-96-7 4-hydroxy-benzoic acid 
• 93-58-3 benzoic acid methyl ester 
• 705254-34-8 potassium trifluoro(4-(methoxycarbonyl)phenyl)borate 
• 171364-80-0 methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate 
• 99768-12-4 4-methoxycarbonylphenylboronic acid 
• 19158-51-1 P-toluenesulfonyl cyanide 

Relevant academic research and scientific papers

Metal-assisted reactions. Mechanism in Heterogeneous Catalytic Transfer Reduction

Hydrogen isotope studies have shown that heterogeneous catalytic transfer hydrogenolysis of C-O bonds in phenolic tetrazolyl ethers, under certain conditions, appears to proceed through a direct transfer of hydrogen from the donor to the substrate.

Intramolecular β-Alkenylation of Cyclohexanones via Pd-Catalyzed Desaturation-Mediated C(sp3)-H/Alkyne Coupling

Site-selective C-C bond formation through the direct coupling of C(sp3)-H bonds with unsaturated hydrocarbons represents an atom-economical and redox-neutral way to functionalize chemically inert positions, such as those β to a carbonyl group. While most existing β-functionalization methods utilize a directing group (DG) strategy, here we report a Pd-catalyzed intramolecular β-alkenylation of ketones using alkynes as the coupling partner without the aid of DGs. Mediated by a ketone desaturation process, the reaction is redox-neutral and avoids using strong acids or bases. The resulting cis-5,6-fused bicycles can be diversely derivatized with excellent selectivity. Mechanistic studies imply an unusual hydride-transfer chain-like pathway, which involves the cyclometalation of an enyne intermediate and protonation of the resulting Pd enolate followed by an intermolecular hydride transfer through the desaturation of another substrate.

Mechanistic studies into visible light-driven carboxylation of aryl halides/triflates by the combined use of palladium and photoredox catalysts

The reaction mechanism of palladium-catalyzed visible light-driven carboxylation of aryl halides and triflates with a photoredox catalyst was examined in detail. Experimental and theoretical studies indicated that the active species for photoredox- catalyzed reduction was cationic ArPd(II)+ species to generate nucleophilic ArPd(I) or its further reduced ArPd(0)- species, which reacted with CO2 to give carboxylic acids. Hydrodehalogenated compounds, main byproducts in this carboxylation, were thought to be generated by protonation of these reduced species.

Organophotoredox assisted cyanation of bromoarenes: via silyl-radical-mediated bromine abstraction

The insertion of a nitrile (-CN) group into arenes through the direct functionalization of the C(sp2)-Br bond is a challenging reaction. Herein, we report an organophotoredox method for the cyanation of aryl bromides using the organic photoredox catalyst 4CzIPN and tosyl cyanide (TsCN) as the nitrile source. A photogenerated silyl radical, via a single electron transfer (SET) mechanism, was employed to abstract bromine from aryl bromide to provide an aryl radical, which was concomitantly intercepted by TsCN to afford the aromatic nitrile. A range of substrates containing electron-donating and -withdrawing groups was demonstrated to undergo cyanation at room temperature in good yields.

Photoinduced catalyst-free deborylation-deuteration of arylboronic acids with D2O

Herein, novel photoinduced catalyst-free deborylation-deuteration of arylboronic acids with D2O is reported. The protocol was compatible with a variety of functionalities, including halogen, alkoxy, cyano, sulfonyl, trimethylsilyl, trifluoromethoxy, alkyl, hydroxyl, free acid, amide, and heteroaromatic rings. A wide range of deuterated products were obtained in good yields with a high level of deuteration. This method provides a green and practical pathway to synthesize deuterium labelled compounds under mild conditions.

Hydrogen bonding promoted simple and clean photo-induced reduction of C-X bond with isopropanol

We herein report a simple and clean photo-induced metal-free reduction of C-X bond under an atmosphere of air at room temperature. Isopropanol is used as both the reducing reagent and solvent. Various functional groups (acids, esters, alcohols, anilines, phenols, indoles, pyridines, cyano and trifluoromethyl groups) and other heterocyclic compounds are tolerated. Different organic halides (including C-I, C-Br and C-Cl bonds) can be dehalogenated with moderate to excellent yields. Polyhalides are also reduced chemoselectively and efficiently. DFT calculation suggests a six-membered ring transition state via C-X H-O hydrogen bonding to decrease the activation energy.

Hydro/deutero deamination of arylazo sulfones under metal and (photo)catalyst-free conditions

Hydrodeaminated and monodeuterated aromatics were obtained via a visible-light driven reaction of arylazo sulfones. Deuteration occurs efficiently in deuterated media such as isopropanol-d8 or in THF-d8/water mixtures and exhibits a high tolerance to the nature and the position of the aromatic substituents.

A highly reducing metal-free photoredox catalyst: Design and application in radical dehalogenations

Here we report the use of 10-phenylphenothiazine (PTH) as an inexpensive, highly reducing metal-free photocatalyst for the reduction of carbon-halogen bonds via the trapping of carbon-centered radical intermediates with a mild hydrogen atom donor. Dehalogenations were carried out on various substrates with excellent yields at room temperature in the presence of air.

Selective Reduction of Aryl Halides and α,β-Unsaturated Esters with Sodium Borohydride-Cuprous Chloride in Methanol and Its Application to Deuterium Labeling

A reducing system, NaBH4-Cu2Cl2/MeOH, was developed for dehalogenation of aryl halides, conjugate reduction of α,β-unsaturated esters, and deuterium labeling in a chemo- and regioselective manner.These reactions proceeded without reduction of isolated olefins.The Cu2Cl2 is assumed to function as the catalyst which generates a transient species of copper hydride as an active reducing agent, on contact with NaBH4.Deuterium-labeling studies indicated that (i) the hydrogen which is transferred to the 4-position of methyl 4-iodobenzoate originates from MeOH and (ii) thehydrogens which were transferred to the α- and β-positions of the conjugated ester originate from MeOH and NaBH4, respectively.

CONVENIENT METHOD FOR DEHALOGENATION OF ARYL HALIDES

Reductive dehalogenation of aryl halides was achieved using hydrogen and a palladium catalyst.By using deuterium gas, the deuterated arenes were readily prepared.