Hydroaminomethylation of oleochemicals: A comprehensive overview

The present review explores the historical background of the rhodium‐catalyzed hydroaminomethylation (HAM) of vegetable oils and the recent developments in this field. The reaction conditions are especially discussed and commented upon. Various amines have been grafted onto alkyl chains of vegetable oils, thus giving rise to a wide range of bio‐based HAM‐products. A focus is on bifunctional HAM‐products as they have potential as monomers in polymer chemistry. The nature of the ligands stabilizing the rhodium catalytic species is also discussed. The catalytic results obtained with phosphanes and amines are analyzed and compared. The goal of this review is to convince the reader that HAM of vegetable oils is a simple and effective synthetic pathway to access valuable functionalized bio‐based compounds with industrial potential. Practical applications: Products resulting from hydroaminomethylation of vegetable oils have potential as monomers in polymer chemistry and as bio‐based surface‐active agents. The functionalization of the carbon–carbon double bonds of vegetable oils by amino groups is easily carried out via rhodium‐catalyzed hydroaminomethylation (HAM). The functionalization of the carbon–carbon double bonds of vegetable oils by amino groups is easily carried out via rhodium‐catalyzed hydroaminomethylation (HAM).