D. A. Evans Charge Affinity Patterns and the Nitro Functional Group Chem 206 Some Reactions of the Nitro Functional Group The Nef reaction R Overall Transformation: 1)HO +N一CH=CHR EtOH R nitronate anion nitronic acid O2N R3N N-H H20 O2N. Et-NH The charge affinity patterns represented R Important Transformations of the -NO2 Functional Group HO H2 ■ Reduction n is quite facile o2N-c(-) Pd, Ni Pt etc R NH Synthesis 1986 ■ Nef reaction a The resonance features which have been exploited VV X=OR, NR2 Org. Reactions 1990, 38, 655 R(+H R(-)H O2N-C(-)O H R R O R H R + + + N R R HO HO + N – O HO R R O R R H2O + N HO HO R R + N R R HO – O R H N X: O2N C(+) O2N C(–) H2O N HO HO R R OH + N R R – O – O + N R R O – O H O2N C(–) OH N R R HO HO + N – O – O R R R H N X: + N H – O O R R + N R R O – O H O2N C(+) N X: R H N H HO HO NO2 R O R OH R NO2 O2N Me O CO2Me Me N H O2N EtOH EtOH Et–NH2 EtOH EtOH O R O NH2 R O O R O H R O O2N O2N H2 R3SnH D R NO2 R NO2 MeO Me O O NO2 R O O R NO2 + N CH CH R –O O D. A. Evans Chem 206 (+) R3N (+) (–) (+) R3N R3N (–) (+) (–) (+) Some Reactions of the Nitro Functional Group ■ Nef Reaction: HO – H3O + rxn is quite facile Pd, Ni, Pt etc ■ Reduction: Important Transformations of the -NO2 Functional Group - H + H + nitronic acid ■ Mechanism ■ Overall Transformation: H HO + – nitronate anion 1) HO – 2) H3O + The Nef Reaction ✔✔ ✔✔ ■ The resonance features which have been exploited: (+) (+) (–) (–) X = OR, NR2 (+) (±) (+) (±) (–) The charge affinity patterns represented nitronate anion HO – H + nitronic acid H + - H + Charge Affinity Patterns and the Nitro Functional Group Pinnick, Org. Reactions 1990, 38, 655 Ono, N.; Kaji, A. Synthesis 1986, 693