Nitroalkanes as Key Compounds for the Synthesis of Amino Derivatives

Abstract

The carbanion stabilizing effect of the nitro group makes nitroalkanes ideal reagents in carbon-carbon bond formation. Once introduced in a molecular framework, the nitro group is amenable to further transformations including reduction to primary amines. The aim of this review is to explore the utilization of nitroalkanes as effective substrates for the preparation of important target compounds featured by the amino group. These will include simple primary amines, diamines, amino acids, piperidines, pyrrolidines and heteroaromatic derivatives. A particular emphasis will be placed on the synthesis of enantioenriched amino derivatives mediated by organocatalysts or organometallic complexes.

Toward Bis C,C‐Glycosyl Compounds and Anomeric γ‐Glycoamino Acids through Michael Addition Reaction of Nitromethane on Z/E Push‐Pull Sugar Olefins

“…Conjugate addition reactions and more particularly the Michael addition reaction is a well‐defined process for carbon–carbon bond formation in organic synthesis 1. Among the reactions studied, the conjugate addition of nitroalkanes to α,β‐unsaturated systems is of great interest, because the nitro group is prone to many synthetic transformations and is easily transformed into amine, nitrile oxide, ketone or carboxylic acid groups to provide a wide range of synthetically interesting compounds 2. Accordingly, the development of enantioselective catalytic protocols for this reaction has attracted considerable attention 3…”

“…The use of nitroalkanes as a source of stabilized carbanions is largely documented in the conjugate addition reaction to electron‐poor alkenes,2,4 and radical additions of stabilized nitromethyl radicals has been described with electron‐rich alkenes such as 1,2‐glycals 5. The use of enantiomerically pure Michael acceptors with a chiral center in the γ‐position that bear an oxygen atom has already been studied 6.…”

“…The 1,4‐addition of a nitromethane anion affords nitro esters in a highly diastereoselective manner. After the addition process, suitable transformation of the nitro group,2 in particular reduction to a primary amine, was carried out to give the corresponding sugar γ‐amino acid building blocks.…”

Keratin Protein-Catalyzed Nitroaldol (Henry) Reaction and Comparison with Other Biopolymers

“…In addition, the reaction can be scaled up (i.e., 1 mmol of 1a) without detriment on the product yield. On the other hand, the nitroaldol (Henry) reaction is a highly versatile C-C bond-forming reaction between an aldehyde or ketone and a nitroalkane to yield β-nitroalcohols, which can be easily modified into valuable building blocks [13][14][15][16][17]. As part of one of our research programs devoted to understanding the potential catalytic role of different biopolymers [18][19][20][21], we report here for the first time the catalytic properties of keratin protein towards the nitroaldol (Henry) reaction as well as a critical comparison with the performance of other natural polymers in the same process.…”

β‐Nitroacrylates: A Versatile and Growing Class of Functionalized Nitroalkenes

“…The high electrophilicity of β‐nitroacrylates makes these compounds suitable substrates for the functionalization of pyrroles and indoles at the C‐2 and C‐3 positions, respectively. In particular, the possibility to reduce the nitro group into the corresponding amino group opens valuable synthetic pathways for producing a wide range of tryptamines under very mild reaction conditions.…”