38405-81-1

Upstream product

• 110-91-8 morpholine 
• 4786-20-3 crotononitrile 
• 4786-20-3 but-2-enenitrile 
• 109-75-1 but-3-enenitrile 

Downstream Products

• 656810-30-9 2-(4-benzyloxy-3-methoxy-benzyl)-3-oxo-butyronitrile 
• 767240-85-7 3-morpholinobutanoic acid 
• 656810-32-1 C₂₅H₂₃NO₃ 
• 410535-87-4 3-oxo-2-(3,4,5-trimethoxy-benzyl)-butyronitrile 

Relevant academic research and scientific papers

Asymmetric catalytic hydroamination of activated olefins in ionic liquids

The addition of a series of both aliphatic and aromatic amines to electron-poor olefins was investigated using [Ni(Pigiphos)(THF)]2- as catalyst (with different counterions) in various ionic liquids based on imidazolium- and picolinium-salt der

Selective and nonselective aza-michael additions catalyzed by a chiral zirconium bis-diketiminate complex

Reaction of the chiral bis-diketiminate complex rac- or (R,R)-C 6H10(nacnacXyl)2ZrCl2 with AgOTf yielded the corresponding bis-triflate complex. The complex geometry changes from distorted octahedral in the dichloride complex to a pseudotetrahedral coordination involving π coordination of the diketiminate ligands. The bis-triflate complex is highly active for aza-Michael additions with turnover frequencies of 20000/h for the addition of morpholine to acrylonitrile and 1000/h for the addition of morpholine to methacrylonitrile. The enantioselectivities of the latter reaction in various solvents were low, never surpassing 19% ee. The reaction is first-order in olefin concentration and second order in amine concentration, which is explained by its participation as a base in the reaction mechanism. The presence of catalytic amounts of triethylamine slightly increases the observed rate constants and reduces the reaction order in amine to first order. Other activated alkenes such as methacrylonitrile, crotonitrile, methyl acrylate, and cyclohexenone can be employed, but no reactivity is observed toward styrene or vinyl ethers. Primary amines, secondary amines, and anilines can be employed as nucleophiles with activities correlating with their nucleophilicity, but the catalyst is unstable in the presence of alcohols.

Hydroamination and alcoholysis of acrylonitrile promoted by the pincer complex {κP,κC,κP-2,6- (Ph2PO)2C6H3}Ni(OSO 2CF3)

This report describes the catalytic activity of the pincer-type complex {κP,κC,κP-2,6-(Ph 2PO)2C6H3}Ni(OSO2CF 3) (1) in the anti-Markovnikov addition of aliphatic and aromatic amines and alcohols to acrylonitrile, crotonitrile, and methacrylonitrile. The influence of additives on the catalytic activities was investigated, and it was found that substoichiometric quantities of water promoted the C-N bond forming reactions catalyzed by 1, especially the reactions involving aromatic amines; in comparison, NEt3 had a less dramatic impact. The opposite pattern was observed for the alcoholysis of acrylonitrile promoted by 1: water had no beneficial effect on these reactions, while NEt3 proved to be a potent promoter. Another important difference between these reactions is that hydroamination works better with more nucleophilic amines, whereas the alcoholysis reactions work well with ArOH, CF3CH2OH, and ArCH2OH but not at all with the more nucleophilic aliphatic alcohols methanol, ethanol, and 2-propanol. Both hydroamination and alcoholysis proceed much better with acrylonitrile in comparison to its Me-substituted derivatives crotonitrile and methacrylonitrile. Under optimized conditions, precatalyst 1 promotes conjugate additions to acrylonitrile with catalytic turnover numbers of up to 100 (hydroamination) or higher (alcoholysis). Spectroscopic studies have established that the main Ni-containing species in the hydroamination reactions is a cationic adduct in which the olefinic substrate is bound to the Ni center via its nitrile moiety; this binding activates the double bond toward an outer-sphere nucleophilic attack by the amine (Michael addition). The solid-state structures of the cationic nitrile adducts [{κP, κC,κP-2,6-(Ph2PO)2C 6H3}Ni(NCR)][OSO2CF3] (R = Me (2a), CH2CH2N(H)Ph (2e)), which can be regarded as model complexes for the species involved in the hydroamination catalysis, have been elucidated. Also reported are the solid-state structures of the charge-neutral compound {κP,κC,κP-2,6-(i- Pr2PO)2C6H3}Ni(OSO 2CF3) and an octahedral Ni(II) species resulting from the aerobic/hydrolytic oxidation of 1.

Addition of amines and phenols to acrylonitrile derivatives catalyzed by the POCOP-type pincer complex [{κP,κC, κP-2,6-(i-Pr2PO)2C6H 3}Ni(NCMe)][OSO2CF3]

The pincer-type complex [{κP,κC, κP-2,6-(i-Pr2PO)2C6H 3}Ni(NCMe)][OSO2CF3] (1) can serve as a precatalyst for the regioselective, anti-Markovnikov addition of nucleophiles to activated olefins. The catalyzed additions of aliphatic amines to acrylonitrile, methacrylonitrile, and crotonitrile proceed at room temperature and give quantitative yields of products resulting from the formation of C-N bonds. On the other hand, aromatic amines or alcohols are completely inert toward methacrylonitrile and crotonitrile, and much less reactive toward acrylonitrile, requiring added base, heating, and extended reaction times to give good yields. The catalytic reactivities of 1 are thought to arise from the substitutional lability of the coordinated acetonitrile that allows competitive coordination of the nitrile moiety in the olefinic substrates; this binding enhances the electrophilicity of the CC moiety, rendering them more susceptible to attack by nucleophiles. In some cases, RCN → Ni binding results in double bond isomerization/migration (allyl cyanide) or attack of nucleophiles at the nitrile moiety (cinnamonitrile and 4-cyanostyrene). Reaction of morpholine with 1 at 60 °C led to formation of the amidine derivative 2 that has been characterized by X-ray crystallography.

Asymmetric hydroamination of acrylonitrile derivatives catalyzed by Ni(II)-complexes

Chiral ferrocenyl tridentate phosphine ligands were synthesized and used in asymmetric hydroamination reactions catalyzed by Ni(II)-complexes. Compounds of the type [Ni(PPP)L]2+, where L is a chloride, solvent molecule or a coordinated substrate, were isolated. The efficiency of these complexes in asymmetric catalysis was high when aliphatic or aromatic amines were reacted with electron-poor olefins, especially with acrylonitrile derivatives. This hydroamination reaction affords up to 95% enantioselectivity at -80 °C for the addition of morpholine to methacrylonitrile (69% ee at room temperature).

Ni(II) complexes containing chiral tridentate phosphines as new catalysts for the hydroamination of activated olefins

Ni(II) complexes containing chiral tridentate ferrocenyl phosphines (Ni(PPP)) have been found to efficiently catalyse the hydroamination of activated olefins with both anilines and aliphatic amines at r.t. (TON up to 71, TOF up to ca. 3 h-1, and enantioselectivities up to 69% ee).