Nitro groups s. a. under

Hu, Y., Yu, J., Yang, S., Wang, J., and Yin, Y. 1999. Substitution reaction of nitro group on a-nitrostyrene by organozinc halides under microwave irradiation. Synthetic Communications, 29 1157-64. 

A ligand-free Suzuki coupling protocol indicates employment of Pd(OAc)2 in PEG-400, in which nanoparticles of Pd are generated in situ. More conventionally, NaOMe is used as a base for coupling at room temperature. Under certain coupling reaction conditions reduction of nitro group(s) also occurs, ... 

We have already pointed out that under these conditions, the true catalytic species is Ru(CO)3(To1-B1AN).R In this complex, the metal atom should be much more basic than in Ru(CO)s or Ru3(CO)i2, thus facilitating electron transfer from the metal to the nitro group. Such a process is now emerging as a common feature of the interaction of organic nitro compounds with low oxidation-state transition metal complexes. ... 

Selective reduction. A suspension of 2-amino-4-benzoxylamino-5-nitro-6-methyl-pyrimidine (prepn. s. 383) in ethanol and coned, aq. NH3 satd. with H2S, and refluxed 30 min. 2,4-diamino-5-nitrO 6-methylpyrimidine. Y 73%.—The benzoxyl group is easily reduced under neutral or alkaline conditions where hydrolysis does not occur. Also with simultaneous reduction of the nitro group s. E. C. Taylor and J. W. Barton, J. Org. Chem. 24, 127 (1959). 

More than twenty years ago, Nesmeyanov s group showed that chlorine can be substituted by a variety of nucleophiles in FeCp(r 6-PhCl)+ [83, 84]. Indeed the chlorine substituent in the chlorobenzene (even) ligand is 1000 times more reactive than when it is located on the cyclopentadienyl (odd) ligand [85]. The FeCp+ is a good withdrawing group which is equivalent to two nitro groups in terms of activation. The reactions proceed under ambient conditions with primary or secondary amines and have been extended to other substituted chloroarene complexes [86, 87] Eq. (22), Table 2. 

The anion of nitromethane is particularly reactive in S l reactions. Various kinds of tertiary nitro groups are replaced by a nitromethyl group on treatment with the anion of nitromethane (Section 7.1).49 2-Iodoadamantane reacts with the anion of nitromethane in the presence of acetone enolate (entrainment reaction) under irradiation of a 400-W UV lamp to give 2-ni-tromethyladamantane in 68% yield, (see Eq. 5.32).50a 1-Iodoadamantane also reacts with the anion of nitromethane in a similar way.50b... 

A double reduction was achieved under catalytic hydrogenation conditions to open the epoxide and reduce the nitro group to an amino group in 90% yield. The aniline thus afforded was reacted with diethylethoxymethylenemalonate to give 92. 92 was next cyclized to the 1,4-benzoxazine 93 via a Mitsunobu reaction in the absence of a Lewis acid, unlike Kim s approach (Kang et al., 1996). Completion of the tricycle core was ultimately achieved in PPE at 140-145°C to furnish the LVX core in 85% yield. The core was converted to LVX (1) in two precedented steps. 

Because of the ability of some leaving groups to stabilize an a-carbanion, the pH at which the substitution is performed can be critical. Electrophiles with such leaving groups (e.g. R-N02 [36, 37], R-S(=0)2R [38, 39], R-S(=O)R[40]) will usually undergo substitution only under neutral or acidic conditions, what limits the choice of suitable nucleophiles. Some nucleophilic displacements of nitro and sulfonyl groups, both under acidic and basic reaction conditions, are shown in Schemes 4.6 and 4.7. Allylic nitro groups can also be readily displaced by catalysis with palla-... 

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