60947-45-7

Upstream product

• 6125-24-2 2-Phenylnitroethane 
• 100-39-0 benzyl bromide 
• 620-05-3 iodomethylbenzene 
• 5153-67-3 nitrostyrene 
• 6921-34-2 benzylmagnesium chloride 
• 180069-62-9 benzylmanganese(II) chloride 
• 103-63-9 1-phenyl-2-bromoethane 
• 102-96-5 (2-nitroethenyl)benzene 
• 62673-31-8 benzyl(bromo)zinc 

Relevant academic research and scientific papers

Solvent- and catalyst-free conjugate additions of organozinc to β-nitroalkene

Conjugate addition of allylzinc and benzylzinc reagents to β-nitroalkenes was carried out without solvent and catalyst at room temperature to give products in high yield. Georg Thieme Verlag Stuttgart.

Solvent-free, one-pot conjugate addition of benzyl bromides to β-nitroalkenes mediated by magnesium powder

A convenient and efficient methodology for conjugate addition of benzyl bromides to β-nitrostyrenes mediated by magnesium powder in one pot under solvent-free conditions at 0 °C has been developed. Advantages of this method are excellent yields, short rea

Generation of nitroalkanes, hydroximoyl halides and nitrile oxides from the reactions of β-nitrostyrenes with Grignard or organolithium reagents

The β-nitrostyrenes 1 or 2 react with Grignard or organolithium reagents in ether or THF solution to generate by 1,4-addition the intermediate nitronates A. When A is treated with dilute hydrochloric acid, high yields of the nitroalkanes 3 (and oximes 4) or 5 are obtained Hydroximoyl halides 6, 8 or nitrile oxides 7 can be isolated when the intermediate A is slowly added to the ice cold concentrated hydrohalic acid. The same products 6 and/or 7 are observed if the nitronates, generated from the substrate 1a, are added to 85% aqueous H2SO4 but only the hydrolyzed carboxylic acids 9 are generated when the β-nitrostyrenes 2 are reacted with Grignard reagents and worked up under the same condition. The nitrile oxides 7 can undergo 1,3-dipolar cycloaddition with alkenes or alkynes to generate 2-isoxazolines or isoxazoles. A one-pot synthesis of the [n,3,0] bicyclic (n = 3 or 4) compounds 23-27 by intramolecular nitrile oxide-olefin cycloadditions is reported.

Additions of organomanganese reagents to conjugated nitroolefins

Additions of organomanganese reagents to aromatic and aliphatic conjugated nitroolefins were examined for the first time. In most cases reaction proceeded rapidly at -30°C. Unlike Mn reagents lacking β-hydrogens (Me, Ph), which lead to oxidative coupling and reductive dimerisation of nitrostyrenes, benzylmanganese chloride gives 1,4-addition in yields exceeding Grignard or Cu-assisted additions. At 0°C alkyl(Bu, Pr)-manganese reagents undergo an addition-migration-elimination process with nitrostyrenes providing a convenient and stereospecific entry into arylated trans-olefins.