Nitro alkanes arylation

The effect of temperature on the reduction of nitro-alkanes has been extensively exploited in the synthesis of cp-ephedrine analogues [i5,21,22] starting from 1-aryl-2-nitropropenes which are easily converted to the substrates 2. Reduction of these nitrocompounds below 20° C affords the hydroxylamine. The amine is formed above 55° C. Neutralisation of either reaction mixture causes rapid intramolecular migration of the acetyl group from oxygen to nitrogen, a reaction which implies a... 

Bei der Hydrierung von aromatischen bzw. heteroaromatischen Nitro-alkenen mit in situ aus Benzaldehyd und 1,2-Diamino-benzol in Butanol hergestelltem 2-Phenyl-2,3-dihydro-benzimidazol werden keine Nebenprodukte gebildet und man erhalt selektiv l-Aryl-2-nitro- bzw. l-Hetaryl-2-nitro-alkane in Ausbeuten von 70-90% ... 

Die Addition von Lithium-organocupraten an l-Aryl-2-nitro-l-alkene liefert a-Aryl-/ -nitro-alkane (12—79%)1 ... 

Apart from linear unfunctionalized nitroalkanes, various other prochiral nitro-alkanes bearing aryl, alcohol, ether, and ester groups also participate effectively in reactions promoted by 25, producing syw-P-nitroamines in good yields and high enantiomeric excesses [32], The utility of this methodology was demonstrated by the synthesis of the neurokinin-1 receptor antagonist CP-99,994 (Scheme 29.14). 

From To - Alkanes Cycloalkanes Alkenes Alkynes Aryls Halogen compounds Alcohols Phenols Ethers, Quinones B. and Si compounds P and 6i compounds Nitro, Nitroso, Azo, Azoxy, Hydrazo, ides Amines Organometallic Aldehydes Ketones Acids, Anhydrides, Esters Arn.des, Amidines, Nitriles Hydroky-aldehydes Amino Heterocycles Nucleosides Miscellaneous, including heterocycles... 

There has been much interest in the reactivity of nitronium salts, for example, toward amides in acetonitrile,the oxidation of alkanes in acetonitrile (via a carbenium ion intermediate),and toward organic sulfides, phosphines, arsines, and stibines. Reaction with diaryl, aryl alkyl, and dialkyl sulfides give sulfoxides, but a few percent of the ring C-nitro products were found for diphenyl sulfide. This is a result of the equilibrium between nitrito onium ions ] X-ONO and nitronium ions This is the first demonstration of the ambident reactivity... 

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