29640-03-7

Upstream product

• 673-32-5 1-Phenylprop-1-yne 
• 104-94-9 4-methoxy-aniline 
• 93-55-0 1-phenyl-propan-1-one 
• 121-97-1 4-Methoxypropiophenone 
• 925-90-6 ethylmagnesium bromide 

Downstream Products

• 22920-61-2 (rac)-4-methoxy-N-(1-phenylpropyl)benzenamine 

Relevant academic research and scientific papers

Iron-catalysed 1,2-aryl migration of tertiary azides

1,2-Aryl migration of α,α-diaryl tertiary azides was achieved by using the catalytic system of FeCl2/N-heterocyclic carbene (NHC) SIPr·HCl. The reaction generated aniline products in good yields after one-pot reduction of the migration-resultant imines.

An umpolung reaction of α-iminonitriles and its application to the synthesis of aminomalononitriles

An umpolung N-alkylation reaction of α-iminonitriles with Grignard reagents affords the corresponding N-alkylated α-aminonitriles in good yields. Subsequent oxidation and cyanation of the N-alkylated products proceeds effectively to give aminomalononitriles in good yields, and the presence of dichlorodimethylsilane as an additive is crucial for obtaining the optimum yield. Furthermore, an electrophilic addition reaction of the intermediate halomagnesium vinylideneamide is shown to give the alkylated and acylated products in good yields.

Efficient Synthesis of Amines by Iron-Catalyzed C=N Transfer Hydrogenation and C=O Reductive Amination

Here we report the catalytic transfer hydrogenation (CTH) of non-activated imines promoted by a Fe-catalyst in the absence of Lewis acid co-catalysts. Use of the (cyclopentadienone)iron complex 1, which is much more active than the classical ‘Kn?lker complex’ 2, allowed to reduce a number of N-aryl and N-alkyl imines in very good yields using iPrOH as hydrogen source. The reaction proceeds with relatively low catalyst loading (0.5–2 mol%) and, remarkably, its scope includes also ketimines, whose reduction with a Fe-complex as the only catalyst has little precedents. Based on this methodology, we developed a one-pot CTH protocol for the reductive amination of aldehydes/ketones, which provides access to secondary amines in high yield without the need to isolate imine intermediates. (Figure presented.).

Asymmetric hydrogenation of N-alkyl and N-aryl ketimines using chiral cationic Ru(diamine) complexes as catalysts: The counteranion and solvent effects, and substrate scope

Asymmetric hydrogenation of N-alkyl and N-aryl ketimines catalyzed by chiral cationic η6-arene-(N-monosulfonylated diamine) Ru(II) complexes has been investigated. Strong counteranion and solvent effects on the enantioselectivity were observed. The ruthenium catalyst bearing non-coordinating BArF- anion was found to be particularly effective for the hydrogenation of acyclic and exocyclic N-alkyl ketimines in the presence of (Boc)2O in dichloromethane or even under solvent-free conditions, providing chiral amines with up to >99% ee and full conversions. Alternatively, the ruthenium catalyst bearing achiral phosphate anion together with corresponding phosphoric acid as the additive was also efficient for the hydrogenation of N-alkyl ketimines in the absence of (Boc)2O with excellent enantioselectivities and full conversions. For N-aryl ketimines lower enantiomeric excesses were observed by using the ruthenium catalyst bearing BArF- anion. This catalytic protocol thus provides a facile and practical access to optically active amines and has been successfully employed in the gram-scale synthesis of enantiomerically pure (+)-sertraline.

Asymmetric reduction of ketimines with trichlorosilane employing an imidazole derived organocatalyst

Organocatalysts for the asymmetric reduction of ketimines are presented that function well at low catalyst loadings providing chiral amines in good yield and enantioselectivity, the latter appearing to be independent of the ketimine substrate geometry.

Asymmetric reduction of imines with trichlorosilane, catalyzed by sigamide, an amino acid-derived formamide: Scope and limitations

(Chemical Equation Presented) Enantioselective reduction of ketimines 6-10 with trichlorosilane can be catalyzed by the N-methyl valine-derived Lewis-basic formamide (S)-23 (Sigamide) with high enantioselectivity (≤97% ee) and low catalyst loading (1-5 mol %) at room temperature in toluene. The reaction is efficient with ketimines derived from aromatic amines (aniline and anisidine) and aromatic, heteroaromatic, conjugated, and even nonaromatic ketones 1-5, in which the steric difference between the alkyl groups R1 and R 2 is sufficient. Simple nitrogen heteroaromatics (8a,b,d) exhibit low enantioselectivities due to the competing coordination of the reagent but increased steric hindrance in the vicinity of the nitrogen (8c,e) results in a considerable improvement. Cyclic imines 32d-d exhibited low to modest enantioselectivities.

Triazole-Au(I) complexes: A new class of catalysts with improved thermal stability and reactivity for intermolecular alkyne hydroamination

(Chemical Equation Presented) A series of 1,2,3-triazole-bound cationic Au(I) catalysts have been synthesized, and their structures have been characterized by X-ray crystallography. Variable-temperature NMR studies revealed dynamic triazole-Au cation coor