Amination, nucleophilic, vicarious

Ar-aminations Nitroarenes undergo amination by vicarious nucleophilic substitution with (Me NNHj) " in DMSO upon addition of r-BuOK. 

Selected substituted thiophene derivatives may also react with nucleophiles. Primary and secondary amines react with 2-bromo-3-substituted-5-nitrothiophenes to produce 11 <95T5403>. Vicarious nucleophilic substitution of hydrogen (VNS) works generally for both 2-nitro- and 3-... 

The nitroazoles are widely used in the reaction of vicarious nucleophilic substitution of hydrogen. Vicarious nucleophilic C-amination is, practically, the single method of direct introduction of the amino group into nitro compounds. Using the vicarious nucleophilic substitution reaction we have successfully carried out the C-amination of some representatives of nitrobenzazoles, nitroazoles, and model compounds thereof and studied the structure of aminated products and the C-amination mechanism [673-678],... 

First the mechanism of vicarious nucleophilic substitution of hydrogen in nitroazoles and nitrobenzene has been discussed in terms of an electron transfer [273-277]. Community of the observed effects in vicarious C-amination of nitroazoles allows... 

Vicarious nucleophilic substitutions. The reagent is useful for introducing an isocyanomethyl group to an o-position of nitroarenes in the presence of r-BuOK in DMF. The products are readily converted into formamides or amines. 

It has recently been shown that Vicarious Nucleophilic Substitution (VNS) can be a useful tool for the synthesis of biologically active compounds containing the l,3,4,5-tetrabenz[cd]indole nucleus, such as 6-methoxy-l,3,4,5-tetrahydrobenz [ cd] indole-4-amine [49]. 

Keywords Alkyl hydroperoxides Amination Ammonia Benzimidazole Benzisoxazole Carbanions Heterocycles Hydroxylation Indole Nitro compounds Nucleophiles Nucleophilic substitution Oxidation Phenazine Potassium permanganate Pyridine Quinoline Sulfones Vicarious... 

Table 3 Amination of six-membered heterocycles and their benzo-fused analogs via the vicarious nucleophilic substitution of hydrogen... 

A variety of methods for the direct amination of nitrobenzene, that do not require halogenated aromatic compounds, have been reported, including both vicarious (eliminative) [16, 17,19,42] and oxidative versions of nucleophilic substitution of hydrogen. Recently, we have described the aminatimi of 1,3-dinitrobenzene promoted by fluoride ions through photochemical activation [43], Also, the use of KMn04 as oxidant is of great practical value [3,44]. 

Vicarious nucleophilic amination with 4-amino-4 -1,2,4-triazoles ArH - ArN<... 

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