74733-36-1

Upstream product

• 34040-64-7 p-methyloxycarbonylbenzyl chloride 
• 590-17-0 cyanomethyl bromide 
• 151937-09-6 3-(4-methoxycarbonylphenyl)propanoic acid 
• 1076-96-6 methyl 4-vinylbenzoate 
• 75-86-5 2-hydroxy-2-methylpropanenitrile 
• 2417-90-5 bromopropionitrile 
• 619-42-1 4-methoxycarbonylphenyl bromide 
• 1679-64-7 Monomethyl terephthalate 
• 107-13-1 acrylonitrile 
• 771559-50-3 2-cyano-3-(4-methoxycarbonylphenyl)propionitrile 
• 113100-81-5 4-(3-oxo-propyl)-benzoic acid methyl ester 
• 1571-08-0 methyl 4-formylbenzoate 
• 1126-46-1 Methyl 4-chlorobenzoate 
• 79430-99-2 (E)-methyl 4-(2-cyanovinyl)benzoate 

Downstream Products

• 223128-06-1 4-(3-benzyloxycarbonylaminopropyl)benzylalcohol 

Relevant academic research and scientific papers

Photochemistry at Scale: Wireless Light Emitters Drive Sustainability in Process Research & Development

Carbon?carbon bond formation by dual Iridium-Nickel photoredox catalysis has gained a lot of attention for late-stage cross-couplings of alkyls with aryls. However, the scalability of such reactions is greatly impeded by the poor light penetration depth into the strongly absorbing reaction media. Wireless internal illumination is a novel technique which circumvents the light penetration issue efficiently and therefore allows to scale photon-driven reactions by conventional methods. Here we demonstrate that industrially relevant photoredox C?C couplings can be scaled seamlessly to different volumes, achieving qualitatively and quantitatively the same results at all scales. The use of conventional reactor types allows stirred, bubble column or fixed-bed operation mode and is fully compatible with heterogeneous reaction mixtures. By minimizing reflection losses, we could also show a significant advantage in the reaction rate over an externally illuminated setup at the same light intensity.

A Titanium-Catalyzed Reductive α-Desulfonylation

A titanium(III)-catalyzed desulfonylation gives access to functionalized alkyl nitrile building blocks from α-sulfonyl nitriles, circumventing traditional base-mediated α-alkylation conditions and strong single electron donors. The reaction tolerates numerous functional groups including free alcohols, esters, amides, and it can be applied also to the α-desulfonylation of ketones. In addition, a one-pot desulfonylative alkylation is demonstrated. Preliminary mechanistic studies indicate a catalyst-dependent mechanism involving a homolytic C?S cleavage.

Upscaling Photoredox Cross-Coupling Reactions in Batch Using Immersion-Well Reactors

Herein we describe a straightforward approach for the scale-up of photoredox cross-coupling reactions from milligram to multigram scale using immersion-well batch reactors with minimal reoptimization of the reaction conditions. This approach can be applied to both homogeneous and, more significantly, heterogeneous reaction mixtures. Furthermore, we have used an immersion-well side-loop reactor to perform a reaction on a 400 mmol scale (86 g of aryl bromide).

Visible- And UV-Light-Induced Decarboxylative Radical Reactions of Benzoic Acids Using Organic Photoredox Catalysts

Photoinduced decarboxylative radical reactions of benzoic acids with electron-deficient alkenes, diborane, and acetonitrile under organic photoredox catalysis conditions and mild heating afforded adducts, arylboronate esters, and the reduction product, respectively. The reaction is thought to involve single-electron transfer promoted the generation of aryl radicals via decarboxylation. A diverse range of benzoic acids were found to be suitable substrates for this photoreaction. Only our two-molecule organic photoredox system can work well for the direct photoinduced decarboxylation of benzoic acids.

Titanium(III)-Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non-Free-Radical Mechanism

A titanium-catalyzed mono-decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. A corresponding desulfonylation is demonstrated as well. Mechanistic experiments support a catalyst-controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations. The involvement of two TiIII species in the C?C cleavage is proposed, and the beneficial role of added ZnCl2 and 2,4,6-collidine hydrochloride is investigated.

Efficient nickel-catalyzed hydrocyanation of alkenes using acetone cyanohydrin as a safer cyano source

An active nickel catalyst prepared in situ from a Ni(II) compound, phosphine ligand, and zinc powder was found to be an efficient catalyst system for the hydrocyanation of various alkenes using acetone cyanohydrin as a safer cyano source. The combination of NiCl2·6H2O and 1,3-bis(diphenylphosphino)propane was the most efficient catalyst precursor in DMF. Under the optimized conditions, various styrenes, heterocyclic alkenes, and aliphatic alkenes were converted to their corresponding nitriles in excellent yields.

Direct Synthesis of Nitriles from Aldehydes Using an O-Benzoyl Hydroxylamine (BHA) as the Nitrogen Source

The direct synthesis of nitriles from commercially available or easily prepared aldehydes has been achieved. O-(4-CF3-benzoyl)-hydroxylamine (CF3-BHA) was utilized as the nitrogen source to generate O-acyl oximes in situ with aldehydes, which can be converted to a nitrile with the assistance of a Bronsted acid. Several aliphatic, aromatic, and α,β-unsaturated nitriles that contain different functional groups were prepared in high yields (up to 94% yield). This method has notable advantages, such as simple and mild conditions, high yields, and good functional group tolerance.

Novel system for the synthesis of nitriles from aldehydes using aqueous ammonia and [bis(trifluoroacetoxy)iodo]benzene

A simple and mild method for the conversion of varieties of aldehydes to the corresponding nitriles using aqueous ammonia and trivalent hypervalent iodine reagent, [bis(trifluoroacetoxy)iodo]benzene, at room temperature is discussed. Advantages of this system are short reaction time, easy workup, and moderate to good yields. Copyright Taylor & Francis Group, LLC.

A novel system for the synthesis of nitriles from aldehydes using aqueous ammonia and sodium dichloroiodate

A simple and mild method for the conversion of varieties of aldehydes to the corresponding nitriles using aqueous ammonia and aqueous sodium dichloroiodate reagent at room temperature is discussed. Advantages of this system are short reaction time, easy work-up and moderate to good yields.

A novel system for the synthesis of nitriles from carboxylic acids

A simple, mild and high yielding method for the conversion of various carboxylic acids to nitriles has been developed using diphosphorus tetraiodide in combination with ammonium carbonate at room temperature.