15429-18-2

Upstream product

• 557-20-0 diethylzinc 
• 780-25-6 N-benzylidene benzylamine 
• 1485-70-7 N-benzylbenzamide 
• 925-90-6 ethylmagnesium bromide 
• 100-46-9 benzylamine 
• 93-55-0 1-phenyl-propan-1-one 
• 10242-40-7 1,1-diethoxy-1-phenylpropane 
• 97-93-8 triethylaluminum 
• 27845-50-7 (E)-N-benzylidenebenzylamine 
• 673-32-5 1-Phenylprop-1-yne 
• 2386-64-3 ethylmagnesium chloride 
• 33542-78-8 N-Benzyl-N-(1-phenyl-propyl)-formamide 
• 859314-73-1 ethyl-(1-phenyl-propenyl)-ether 
• 63459-05-2 N-propylidenebenzylamine 

Relevant academic research and scientific papers

Addition of diethylzinc to imines promoted by Lewis acid

The alkylation of imines by using diethylzinc reagent in the presence of Lewis acid afforded secondary amines in high yield.

Grignard reagent mediated reaction of Cp2Zr(II)-ethylene complex with imines

Imines which do not react with Grignard reagents reacted with EtMgBr in the presence of a catalytic amount of Cp2ZrCl2 to give ethylated products in excellent yields; the stoichiometric reaction of the imines and the zirconocene-ethy

Iridium-Catalyzed Reductive Alkylations of Secondary Amides

Reported herein is the first direct, metal-catalyzed reductive functionalization of secondary amides to give functionalized amines and heterocycles. The method is shown to have exceptionally broad scope with respect to suitable nucleophiles, which cover both hard and soft C nucleophiles as well as a P nucleophile. The reaction exhibits good chemoselectivity and tolerates several sensitive functional groups.

Iron-catalyzed transfer hydrogenation of imines assisted by an iron-based Lewis acid

An iron-catalyzed transfer hydrogenation of N-aryl and N-alkyl imines using isopropanol as the hydrogen donor is reported for the first time. A combination of two iron complexes serving different roles is the key for the success of this catalytic system. As a result, an environmentally friendly and precious metal-free transfer hydrogenation of imines has been developed. The use of a suitable co-catalyst as an activator not only led to efficient transfer hydrogenation, but also showed potential in enantioselective transformation.

An (Aminopyrimidinato)titanium catalyst for the hydroamination of alkynes and alkenes

A new (aminopyrimidinato)titanium complex has been synthesised from inexpensive and easily accessible 2-(tert-butylamino)pyrimidine and [Ti(NMe 2)4] and used as a catalyst for the intermolecular hydroamination of alkynes as well as the cyclization of aminoalkenes. The hydroamination reactions of 1-phenylpropyne and terminal arylalkynes deliver the corresponding anti-Markovnikov addition products with excellent yields and regioselectivities. A new (aminopyrimidinato)titanium complex has been synthesised from inexpensive 2-(tert-butylamino)pyrimidine and [Ti(NMe 2)4] and used as a catalyst for the intermolecular hydroamination of alkynes as well as the cyclization of aminoalkenes. The complex represents the first example of a catalyst for the hydroamination of alkynes that contains an aminoheteroaromatic ancillary ligand.

Addition of trialkylalanes to imines under zirconium catalysis

Trialkylalanes, which are inert toward imines, undergo addition to them in the presence of a catalytic amount of dichlorodicyclopentadienylzirconium(IV) (Cp2ZrCl2). The reaction tolerates the presence of several functional groups in the starting imine such as halo, amide, nitrile, and hydroxy groups. A possible reaction pathway is proposed involving metallacyclic intermediates. Georg Thieme Verlag Stuttgart.

[Ind2TiMe2]: A general catalyst for the intermolecular hydroamination of alkynes

[Ind2TiMe2] (Ind=indenyl) is a highly active and general catalyst for the intermolecular hydroamination of alkynes. It catalyzes the reaction of primary aryl-, tert-alkyl-, sec-alkyl-, and nalkylamines with internal and terminal alkynes. In the case of unsymmetrically substituted 1-phenyl-2-alkylalkynes, the reactions occur with modest to excellent regioselectivities, whereby formation of the anti-Markovnikov regioisomers is favored. While the major product of hydroamination reactions of terminal arylalkynes is always the anti-Markovnikov isomer, alkylalkynes react with arylamines to preferably give the Markovnikov products. To achieve reasonable rates for the addition of sterically less hindered n-alkyland benzylamines to alkynes, these amines must be added slowly to the reaction mixtures. This behavior is explained by the fact that the catalytic cycle proposed on the basis of an initial kinetic investigation includes the possibility that the rate of the reaction increases with decreasing concentration of the employed amine. Furthermore, no dimerization of the catalytically active imido complex is observed in the hydroamination of 1-phenylpropyne with 4-methylaniline in the presence of [Ind2TiMe2] as catalyst. In general, a combination of [Ind2TiMe2]-catalyzed hydroamination of alkynes with subsequent reduction leads to the formation of secondary amines with good to excellent yields. Particularly impressive is that [Ind 2TiMe2] makes it possible for the first time to perform the reactions of n-alkyl- and benzylamines with 1-phenylpropyne in a highly regioselective fashion.

Cp*2TiMe2: An improved catalyst for the intermolecular addition of n-alkyl- and benzylamines to alkynes

Cp*2TiMe2 has been found to be a competent catalyst for the intermolecular addition of sterically less demanding n-alkyl- and benzylamines to internal alkynes. In the presence of 2.0-6.0 mol % of the catalyst, hydroamination reactions between n-propyl-, n-hexyl-, benzyl-, p-methoxybenzyl- or 2-phenylethylamine and diphenylacetylene, 3-hexyne or 4-octyne go to completion within 24 h or less at 114°C (oil bath temperature). After subsequent reduction of the initially formed imines with zinc-modified sodium cyanoborohydride in MeOH at 25°C, the corresponding secondary amines can be isolated in excellent yields (> 78%). Hydroamination/reduction sequences employing the unsymmetrically substituted alkyne 1-phenylpropyne give access to mixtures of regioisomeric secondary amines. The observed regioselectivity is low.

Zirconium-catalyzed ethylmagnesiation of imines - Scope and mechanism

The title reaction has been developed for a series of aldimines and ketimines. Most notably, ketimines - which are totally inert towards alkyl Grignard reagents in the absence of the zirconium catalyst - react smoothly when 10 mol % of Cp2ZrCl2 is added. The mechanism of the reaction has been studied. The intermediate azazirconacycle proved to react by two competing pathways involving mono- and dimagnesiated final products before hydrolysis.