772-13-4

Upstream product

• 51552-98-8 3-phenylbutanoyl chloride 
• 104192-56-5 (Z)-4-Phenyl-2-trimethylsilanyloxy-but-2-enenitrile 
• 74-88-4 methyl iodide 
• 100573-50-0 (E)-4-phenyl-2-(trimethylsiloxy)but-3-enenitrile 
• 83575-64-8 C₁₃H₁₆LiNOSi 
• 4593-90-2 3-phenylbutyric acid 
• 625-37-6 crotonamide 
• 2996-92-1 phenyl trimethylsiloxane 
• 71-43-2 benzene 
• 853955-69-8 [2-(hydroxymethyl)phenyl]dimethyl(phenyl)silane 
• 14371-10-9 (E)-3-phenylpropenal 
• 704-79-0 3-phenylbut-2-enoic acid 
• 201230-82-2 carbon monoxide 
• 98-83-9 isopropenylbenzene 

Downstream Products

• 38135-56-7 (3-phenyl-n-butyl)-amine 
• 14368-40-2 (Z)-3-phenylbut-2-enenitrile 
• 14368-40-2 (E)-3-phenyl-2-butenenitrile 
• 20132-76-7 3-phenyl-butyronitrile 
• 4593-90-2 3-phenylbutyric acid 

Relevant academic research and scientific papers

A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes

The direct synthesis of amides and nitriles from readily available aldehyde precursors provides access to functional groups of major synthetic utility. To date, most reliable catalytic methods have typically been optimized to supply one product exclusively. Herein, we describe an approach centered on an operationally simple iron-based system that, depending on the reaction conditions, selectively addresses either the C=O or C-H bond of aldehydes. This way, two divergent reaction pathways can be opened to furnish both products in high yields and selectivities under mild reaction conditions. The catalyst system takes advantage of iron's dual reactivity capable of acting as (1) a Lewis acid and (2) a nitrene transfer platform to govern the aldehyde building block. The present transformation offers a rare control over the selectivity on the basis of the iron system's ionic nature. This approach expands the repertoire of protocols for amide and nitrile synthesis and shows that fine adjustments of the catalyst system's molecular environment can supply control over bond activation processes, thus providing easy access to various products from primary building blocks.

Palladium-catalyzed regiodivergent hydroaminocarbonylation of alkenes to primary amides with ammonium chloride

Palladium-catalyzed hydroaminocarbonylation of alkenes for the synthesis of primary amides has long been an elusive aim. Here, we report an efficient catalytic system which enables inexpensive NH4Cl to be utilized as a practical alternative to gaseous ammonia for the palladium-catalyzed alkene-hydroaminocarbonylation reaction. Through appropriate choice of the palladium precursors and ligands, either branched or linear primary amides can be obtained in good yields with good to excellent regioselectivities. Primary mechanistic studies were conducted and disclosed that electrophilic acylpalladium species were capable of capturing the NH2-moiety from ammonium salts to form amides in the presence of CO with NMP as a base.

Primary fatty acid amide preparation method

The present invention provides a primary fatty acid amide preparation method. According to the present invention, under the action of a single auxiliary agent phosphine-containing transition metal catalyst or a combined auxiliary agent comprising a phosphine-free transition metal catalyst and a phosphine-containing ligand, terminally substituted olefin or cyclo-olefin, carbon monoxide and an ammonium salt are subjected to a hydrogen carboamidation reaction so as to prepare the primary fatty acid amide compound in one step; the raw material and the catalyst of the reaction are inexpensive and easy to obtain, and the synthesis process is simple, such that the synthesis cost is substantially reduced; the preparation method has characteristics of mild reaction condition and high yield, and issuitable for industrial production; and the raw material and the catalyst of the reaction are clean, non-toxic and low environment pollution.

Chiral Nanoparticles/Lewis Acids as Cooperative Catalysts for Asymmetric 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Amides

Cooperative catalysts consisting of chiral Rh/Ag nanoparticles and Sc(OTf)3have been developed that catalyze asymmetric 1,4-addition reactions of arylboronic acids with α,β-unsaturated amides efficiently. The reaction has been considered one of

Palladium-Catalyzed α,β-Dehydrogenation of Esters and Nitriles

A highly practical and general palladium-catalyzed methodology for the α,β-dehydrogenation of esters and nitriles is reported. Generation of a zinc enolate or (cyanoalkyl)zinc species followed by the addition of an allyl oxidant and a palladium catalyst results in synthetically useful yields of α,β-unsaturated esters, lactones, and nitriles. Preliminary mechanistic investigations are consistent with reversible β-hydride elimination and turnover-limiting, propene-forming reductive elimination.

Organo[2-(hydroxymethyl)phenyl]dimethylsilanes as mild and reproducible agents for rhodium-catalyzed 1,4-addition reactions

Stable and reusable tetraorganosilicon reagents, alkenyl-, aryl-, and silyl[2-(hydroxymethyl)phenyl]-dimethylsilanes, undergo 1,4-addition reactions to α,β-unsaturated carbonyl acceptors under mild rhodium-catalysis. The reaction tolerates a diverse range of functional groups and is applicable to gram-scale synthesis. Use of a chiral diene ligand allows the achievement of the corresponding enantioselective transformations using the tetraorganosilicon reagents, providing the silicon-based approach to optically active ketones and substituted piperidones that serve as synthetic intermediates of pharmaceuticals. A rhodium alkoxide species is suggested to be responsible for a transmetalation step on the basis of the observed kinetic resolution of a racemic chiral phenylsilane in the enantioselective 1,4-addition reaction under the rhodium-chiral diene catalysis.

Rhodium-catalysed 1,4-addition of diarylindium hydroxides to α,β-unsaturated carbonyl compounds

Diarylindium(III) hydroxides react with α,β-unsaturated carbonyl compounds in the presence of a rhodium catalyst to afford the 1,4-addition products in high yield. This reaction demonstrates the utility of diarylindium(III) hydroxide as an aryl source with rhodium catalysts. The Royal Society of Chemistry 2005.

Friedel-Crafts alkylation of benzene with α,β-unsaturated amides

A variety of α,β-unsaturated amides (RHC=CH 2CONR′2, R=H, Me, Ar; R′=H or Et) readily condense with benzene at room temperature in the presence of an excess of aluminum chloride to give the corresponding 3-phenylpropionamides in excellent yields. This simple, one-pot procedure proved to be efficient and very clean. The mechanism of these and related reactions is discussed and the participation of superelectrophilic dicationic intermediates is suggested.

Superacidic activation of α,β-unsaturated amides and their electrophilic reactions

The electrophilic reactivity of α,β-unsaturated amides towards weak nucleophiles such as arenes and cyclohexane, initiated either with triflic acid (CF3SO3H) or with excess AlCl3, has been studied. The amides generally condense readily with aromatics in the presence of AlCl3 to give 3-arylpropionamides and related compounds in excellent yields, while some amides also undergo selective ionic hydrogenation with cyclohexane to give saturated amides. The proposed mechanism of these reactions involves dicationic intermediates (superelectrophiles). The direct observation of a dicationic species (by low-temperature NMR) is reported. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Conjugate addition of organosiloxanes to α,β-unsaturated carbonyl compounds catalyzed by a cationic rhodium complex

A novel, additive-free, and clean conjugate addition reaction of organosiloxanes to α,β-unsaturated carbonyl compounds catalyzed by a cationic rhodium complex in water-containing solvent has been developed. A plausible reaction mechanism involving the add