Amines industrially relevant amine compounds

Amines, including the amino acids, peptides and proteins, are mentioned in this Section. Tables 1-3 list primary, secondary and tertiary amines of industrial relevance. Compounds... 

Aliphatic amines are amongst the most important bulk and fine chemicals in the chemical and pharmaceutical industry [13]. Hydroaminomethylation of alkenes to amines presents an atom-economic, efficient and elegant synthetic pathway towards this class of compounds. In hydroaminomethylation a reaction sequence of hydroformylation of an alkene to an aldehyde with subsequent reductive amina-tion proceeds in a domino reaction (see Eq. 4) [14]. Recently, the highly selective hydroamination of alkenes with ammonia to form linear primary and secondary aliphatic amines with a new Rh/Ir catalytic system (] Rh(cod)Cl 2], ] Ir(cod)Cl 2], aqueous TPPTS solution) has been described (see Scheme 2) [15]. The method is of particular importance for the production of industrially relevant, low molecular weight amines. 

These palladium-catalyzed amination reactions of haloarenes are among the most popular modern methodologies for C(sp )-N bond formations. A detailed summary on the state of the art of these (also industrially relevant) reactions, as well as of related arylation reactions of a-C—H acidic compounds, is provided in Chapter 3 by Bjorn Schlummer and Ulrich Scholz. 

The Staudinger reduction has found its way into the synthesis of many biologically relevant molecules in both academia and industry. The following example, published in 2004 from scientists at Abbott Laboratories, comes from their work toward synthesizing new famesyltransferase inhibitors. Quinolone 62 is one example from this publication.29 In the synthesis of this particular inhibitor, bromide 59 was reacted with sodium azide to afford the corresponding azide in 70% yield. Addition of an excess of triphenylphosphine to compound 60 in refluxing THF/H2O delivered the desired amine 61 in 83% yield. Reductive animation then afforded the final target compound 62. 

The development of catalytic methods for the hydroamination of nonactivated alkenes, allenes, and alkynes has received considerable attention in recent years [1]. These highly atom-economical processes allow direct access to industrially and biologically relevant classes of compounds such as amines, enamines, and imines from cheap and readily available starting materials. This has recently led to an ever-increasing range of molecular compounds that have been identified as catalysts for these transformations (Scheme 13.1). Whereas rare-earth catalysts have been found to be mainly active in intramolecular hydroamination, other catalysts - in particular those of the late transition metals - are frequently limited to the addition of weakly basic substrates (aniline, sulfonamides, carboxamides, etc.) to alkenes, alkynes, and allenes. 

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