25695-90-3

Upstream product

• 100-52-7 benzaldehyde 
• 108-03-2 1-Nitropropane 
• 634153-60-9 (E)-N-benzylidene-1-(2-methoxyphenyl)methanamine 
• 6329-58-4 Diethyl 1-nitropropanephosphonate 
• 79-24-3 Nitroethane 
• 344347-13-3 2-nitro-1-phenyl-1-trimethylsilyloxybutane 
• 1077-18-5 N-benzylidenebutan-1-amine 
• 126416-05-5 β-pentyl-nitrostyrene 
• 5153-67-3 nitrostyrene 

Downstream Products

• 61668-44-8 1-phenyl-2-nitrobutane 
• 100-52-7 benzaldehyde 
• 123-38-6 propionaldehyde 
• 802294-64-0 propionic acid 
• 1007-32-5 benzyl ethyl ketone 
• 68579-41-9 2,5-diethyl-3,4-diphenyl-pyrrole 

Relevant academic research and scientific papers

Synthesis of N-Heterocycles by Reductive Cyclization of Nitroalkenes Using Molybdenum Hexacarbonyl as Carbon Monoxide Surrogate

The development of a method that uses molybdenum hexacarbonyl [Mo(CO)6] as carbon monoxide (CO) surrogate for the palladium-catalyzed reductive cyclization of nitroalkenes into indoles or thienopyrroles is reported. Several types of nitroalkenes could be transformed into the desired products in excellent yields and in most cases with complete regioselectivities and higher yields than those previously reported with palladium/CO system.

Regioselective Opening of Nitroepoxides with Unsymmetrical Diamines

Nitroepoxides are easily transformed into benzodiazepines, tetrahydrobenzodiazepines, imidazopyridines, and N-alkyl tetrahydroquinoxalines by treatment with 2-aminobenzylamines, 2-aminopyridines, and N-alkyl 1,2-diaminobenzenes, respectively. Regioselectivity is controlled through attack of the most nucleophilic nitrogen of the unsymmetrical diamine to the β position of the epoxide. These reactions represent an efficient way to prepare privileged bioactive structures.

Catalyst- and Substituent-Controlled Switching of Chemoselectivity for the Enantioselective Synthesis of Fully Substituted Cyclobutane Derivatives via 2 + 2 Annulation of Vinylogous Ketone Enolates and Nitroalkene

The first regioselective, diastereoselective, and enantioselective organocatalyzed Michael-Michael cascade of vinylogous ketone enolates and nitroalkenes for the construction of fully substituted cyclobutanes is achieved by the deployment of the appropriate chiral squaramide catalyst and the pertinent substituent on the substrate. The domino reaction provided cyclobutanes with four contiguous stereocenters, including a quaternary center in good yields with diastereomeric ratio of >20:1 and with enantioselectivities of mostly up to 98% enantiomeric excess (ee). The structures and the absolute configurations of the adducts were confirmed by single-crystal X-ray crystallographic analyses of the appropriate products.

Cathodic hydrodimerization of nitroolefins

Nitroalkenes are easily accessible in high variety by condensation of aldehydes with aliphatic nitroalkanes. They belong to the group of activated alkenes that can be hydrodimerized by cathodic reduction. There are many olefins with different electron withdrawing groups used for cathodic hydrodimerization, but not much is known about the behaviour of the nitro group. Synthetic applications of this group could profit from the easy access to nitroolefins in large variety, the C-C bond formation with the introduction of two nitro groups in a 1,4-distance and the conversions of the nitro group by reduction to oximes and amines, the conversion into aldehydes and ketones via the Nef reaction and base catalyzed condensations at the acidic CH bond. Eight 1-aryl-2-nitro-1-propenes have been electrolyzed in an undivided electrolysis cell to afford 2,5-dinitro-3,4-diaryl hexanes in high yield. The 4-methoxy-, 4-trifluoromethyl-, 2-chloro- and 2,6-difluorophenyl group and furthermore the 2-furyl and 2-pyrrolyl group have been applied. The reaction is chemoselective as only the double bond but not the nitro group undergoes reaction, is regioselective as a β,β-coupling with regard to the nitro group and forms preferentially two out of six possible diastereomers as major products.

Enantioselective hydrogenation of α,β-disubstituted nitroalkenes

The first highly chemo- and enantioselective hydrogenation of α,β-disubstituted nitroalkenes was accomplished with rhodium/JosiPhos-J2 as a catalyst, with the yield and enantioselectivity of up to 95% and 94%, respectively. The α-chiral nitroalkanes will provide an entry to valuable chiral amphetamines which are otherwise not so easily accessed. This journal is the Partner Organisations 2014.

Design of phosphorus ligands with deep chiral pockets: Practical Synthesis of chiral β-arylamines by asymmetric hydrogenation

WingPhos, a C2-symmetric bisphosphorus ligand with a deep and well-defined chiral pocket was developed. It has shown high efficiency in the rhodium-catalyzed asymmetric hydrogenation of (E)-β-aryl-N-acetyl enamides, cyclic β-aryl enamides, and heterocyclic β-aryl enamides. A series of chiral β-arylisopropylamines, 2-aminotetralines, and 3-aminochromans can be synthesized with excellent ee values (nbd=3,5-norbornadiene; TON=turnover number). Copyright

Adapting to substrate challenges: Peptides as catalysts for conjugate addition reactions of aldehydes to α,β-disubstituted nitroolefins

Conjugate addition reactions of aldehydes to α,β-disubstituted nitroolefins are important because they provide synthetically useful γ-nitroaldehydes bearing three consecutive stereogenic centers. Such reactions are challenging due to the drastically lower reactivity of α,β-disubstituted nitroolefins compared to, for example, β-monosubstituted nitroolefins. The testing of a small collection of peptides of the type Pro-Pro-Xaa (Xaa=acidic amino acid) led to the identification of H-Pro-Pro-D-Gln-OH and H-Pro-Pro-Asn-OH as excellent stereoselective catalysts for this transformation. In the presence of 5a mol% of these peptides different combinations of aldehydes and α,β- disubstituted nitroolefins react readily with each other providing γ-nitroaldehydes in good yields and diastereoselectivities as well as excellent enantioselectivities. Chiral pyrrolidines as well as fully substituted γ-butyrolactams and γ-amino acids are easily accessible from the γ-nitroaldehydes. Mechanistic studies demonstrate that the configuration at all three stereogenic centers is induced by the peptidic catalysts. Only a minimal amount of products from homo-aldol reactions is observed demonstrating the high chemoselectivity of the peptidic catalysts. α,β- Disubstituted nitroolefins are challenging electrophiles due to their low reactivity. The modular nature of peptides of the type Pro-Pro-Xaa (Xaa=acidic amino acid; see scheme) allowed for the identification of H-Pro-Pro-D-Gln-OH and H-Pro-Pro-Asn-OH as very good catalysts for the conjugate addition reaction of aldehydes to α,β-disubstituted nitroolefins. Mechanistic studies demonstrate that the peptides induce the configuration at each of the stereogenic centers. Copyright

Oxidative cleavage of nitroalkenes with hydrogen peroxide in environmentally acceptable solvents

Hydrogen peroxide serves as an efficient oxidant for the nitroalkene C=C bond cleavage to aldehydes in ionic liquids. Copyright

Scope and limitations of the nitro-Mannich reaction for the stereoselective synthesis of 1,2-diamines

(Chemical Equation Presented) The acetic acid-promoted addition of lithium nitropropanate and the Lewis acid-catalyzed [Sc-(OTf)3, Cu(OTf) 2, or Ti(OiPr)4] addition of trimethylsilyl nitropropanate to a range of heteroaromatic and simple aliphatic aldimines gave anti-rich (～3-19:1) β-nitroamines in >95% yields as the kinetic products. It was found that a nonpolar N-imine protecting group was essential for reactivity with the o-methoxybenzyl (OMB) group giving better selectivities and yields than p-methoxybenzyl (PMB) or p-methoxyphenyl (PMP) in the Lewis acid-catalyzed addition reactions. Reduction with SmI2, treatment with COCl 2, followed by OMB deprotection gave diastereomerically pure cis-imidazolidinones in 55-79% overall yield from imine. Preliminary results have shown that acetic acid can catalyze the reaction of N-OMB-benzylideneamine with nitropropane, used as solvent, to give the thermodynamically more stable syn-β-nitroamine product.

Asymmetric reduction of nitroalkenes with baker's yeast

Various α,β-disubstituted and trisubstituted nitroalkenes were chemoselectively reduced with baker's yeast to the corresponding nitroalkanes. Stereoselectivities of the reduction of α,β-disubstituted nitroalkenes were modest to low, and e.e.s up to 52% were obtained. Trisubstituted nitroalkenes could be reduced to the corresponding nitroalkanes with excellent enantioselectivities, moderate diastereoselectivities and in good yield.