Allylic nitro compounds, reduction

A new synthesis of substituted 1,3-dienes by reductive elimination of allylic nitro derivatives has been reported (Eq. 7.134).180 Tertiary allylic nitro compounds, bearing an acetate group in the (3-position, smoothly undergo reductive elimination to give conjugated 1,3-dienes when treated with chromous acetate and 2,2-dipyridine in DMF at 111-120 °C. 

Denitration of ally lie nitro groups " Allylic nitro compounds when com-plexed with Pd(0) are reductively removed by a variety of hydride donors. The regioselectivity of denitration to give 1- or 2-alkenes can be controlled by the choice of ligand and by the hydride donor. Thus reduction by formates gives 1-alkenes, and use of NaBH4 or NaBH,CN favors formation of 2-alkenes. 

Reduction of nitroalkanes RNO2 with samarium(II) iodide, obtained from samarium and 1,2-diiodoethane, yields either alkylhydroxylamines RNHOH or alkylamines RNH2, depending on the amount of the reagent434. The base-catalysed reaction of nitroalkanes with phenyl(vinyl) sulphoxide (399) yields the conjugate adducts 400, which fragment to allylic nitro compounds 401 on thermolysis435. 

Reductive conversion of allylic nitro compounds into conjugated oximes... 

DeShong (Scheme 20). Thus, reaction of nitrones with vinyl silanes followed by reduction provides Peterson - type intermediates which can then be eliminated to either Z- or E-products. Homoallylic amines were also prepared using allylsilane in the initial cycloaddition. Substitution reactions of allylic nitro compounds have received considerable attention and some examples are outlined in Scheme 21. In each case, examination of the regiochemistry of the reaction was of paramount concern, the results using palladium being superior to the SnCl mediated process. Allylic sulphides constitute yet another group of... 

The requisite hydroxylamine function for such cyclizations can also be generated from a precursor having a nitro group. This novel route has provided access to hitherto unknown l-hydroxy-6-allyl-, and -6,6-bisallyl-piperazine-2,5-diones (91UP1). The starting material is an W-nitroacetyl amino acid ester that can be either mono-or bis-allylated at the methylene adjacent to the nitro group. Reduction of the N02 to NHOH using zinc/ ammonium chloride, followed by cyclization, leads to the desired products (Scheme 76). Compound (215) is unique in that it possesses a chiral center at C-3 and a quaternary carbon at C-6 on a l-hydroxypiperazine-2,5-dione system. 

The most conspicuous property of aliphatic amines, apart from their fishy smell, is their high basicity, which usually precludes N-alkylations under acidic reaction conditions (last reaction, Scheme 6.3). Hence, alkylation of amines with tertiary alkyl groups is not usually possible without the use of highly stabilized carbocations which can be formed under basic reaction conditions. Rare exceptions are N-alkyla-tions of amines via radicals (Scheme 4.2), copper-catalyzed propargylations (Scheme 6.3), and the addition of amines to some Michael acceptors and allyl palladium or iridium complexes. Better strategies for the preparation of tert-alkylamines include the addition of Grignard reagents to ketone-derived imines [13] or the reduction of tert-alkyl nitro compounds. 

The use of nitro arenes as the nitrogen fragment donor in combination with CO under catalytic, and reductive, conditions has also been presented by Nicholas et al. who have found that [CpFe(CO)2]2 can be used as the catalyst [69]. A variety of different alkenes were tested, and a-methyl styrene gave the highest yield of the allyl amine 113 when nitrobenzene was used. The yield of the allyl amine depends markedly on the structure of both the alkene and the nitro compounds. 

The data show that allylboration of aromatic nitro compounds is a complicated process. Ar-Monoallylated and MN-diallylated arylamines are the products of reductive allylboration of the nitro group and diallyl is apparently formed by the recombination of allyl radicals. Surprisingly, allyl alcohol is produced only in a negligible amount (<5%). 

Reductive alkylation of aromatic nitro compounds is possible. The reaction of nitrobenzene with allylic or benzyl hahdes in the presence of an excess of tin metal in methanol, leads to the A,A -diaUyl or dibenzyl aniline. A similar reaction occurs with nitrobenzene, allyl bromide, and indium metal in aq. acetonitrile. 

Associated with some metals (Al, Fe, Zn), BiCl3 gives Bi(0) which is a catalyst for the allylation of aldehydes and amines (ref. 35), and for the reduction of aromatic nitro compounds to azoxy compounds (ref. 36). When associated with sodium borohydride, BiCl3 gives an efficient system for the selective reduction of nitroarenes and azomethines (ref. 37). 

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