Amines nitroalkane coupling with

In 2002, Zhu reported an example of oxidative carbon-carbon coupling catalysed by a gold(iii) complex where air was the sole oxidant (Scheme 16.39). Tertiaiy amines were coupled with nitroalkanes or ketones in the presence of 3 mol% of complex XXm. The reaction was carried out using the corresponding nitroalkane or ketone as solvent and in some cases a small amount of methanol was added. In the case of the coupling with ketones, the addition of 4 A molecular sieves and small amounts of acid were proven to be beneficial for the reaction. Remarkably, this protocol could be scaled up and one of the products was successfully prepared on a 1 g scale. The protocol was expanded to the coupling of tertiary amines and phosphine oxides in a later report by the same group. ... 

Another variant of this reaction has also been described51. In this case, carbonyl compounds were coupled with amines and a,[3-unsaturated nitroalkanes to form 1,3,4,5-alkyl substituted pyrroles on AI2O3 as the solid support, Scheme 5.32. After 15 min irradiation, the products were obtained in 71—86% yield. It was found that substitution at the a-position of the nitroalkane was essential for the reaction. While... 

Scheme 4 Oxidative coupling of tertiary amines with nitroalkanes...

Initial imine or iminium generation from amines can be used to allow C-X (X = heteroatom) or C-C bond formation. Thus, anilines substituted in the orf/zo-position with X-H functionalities (X = 0, NMe, S) have been dehy-drogenatively condensed with benzylamines under mpg-CN photocatalysis to yield the corresponding benzofused heterocycles [122]. Via iminium intermediates, AI-aryl-l,2,3,4-tetrahydroisoquinolines could be dehydrogenatively coupled photocatalytically by mpg-CN to various carbon nucleophiles derived from nitroalkanes, malonates, and 2-alkanones, and the latter via tandem organocatalysis with proline [124]. 

Malt S, Biswas S, Jana U (2010) lron(lII)-catalyzed four-component coupling reaction of 1,3-dicarbonyl compounds, amines, aldehydes, and nitroalkanes a simple and direct synthesis of functionalized pyrroles. J Org Chem 75 1674—1683. doi 10.1021/jo902661y Makosza M, Jagusztyn-Grochowska M, Ludwikow M, Jawdosiuk M (1974) Reactions of organic anions— L reactions of phenylacetonitrile derivatives with aromatic nitrocompounds in basic media. Tetrahedron 30(20) 3723-3735. doi 10.1016/S0040-4020(01)90658-l Mamedov VA, Levin YA (1996) Unexpected reaction of o-phenylenediamine with... 

The success of the sp C-H/sp C-H and sp C-H/sp C-H couplings led us to explore the possibility of the even more challenging CDC reaction between sp C-H and sp C-H bonds. We started with the reaction of an a-sp C-H bond of nitrogen in amines with nitroalkanes, which would provide aza-Henry-type reaction products. Using CuBr as the catalyst and TBHP as the terminal oxidant, various p-nitroamine derivatives were generated by this new methodology (Scheme 1.22). ... 

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