Katalytische Hydroaminomethylierung für die hochselektive Synthese von linearen Fettaminen

Abstract

Ausgehend von höheren Olefinen (>C12) bietet die Rhodium‐katalysierte Hydroamino‐methylierung einen einstufigen und atomeffizienten Zugang zu Fettaminen. Unter optimierten Bedingungen können hohe Katalysatoraktivitäten und ‐produktivitäten erzielt werden und die linearen Produkte mit ausgezeichneter Regioselektivität erhalten werden.

Recent advances in catalytic C–N bond formation: a comparison of cascade hydroaminomethylation and reductive amination reactions with the corresponding hydroamidomethylation and reductive amidation reactions

“…In the following years, most of the reports describe the hydroaminomethylation as a versatile, selective and atomefficient tool for the synthesis of a range of organic compounds, including synthesis of fatty amines from unsaturated fatty acid esters, [90][91][92][93] synthesis of pharmaceuticals compounds 94,95 and synthesis of heterocyclic rings via ring-closing hydroaminomethylation reaction. [96][97][98][99][100][101] The critical step in this sequence is the hydrogenation of the intermediate imino compounds, which is generally hampered by the presence of carbon monoxide; however, over the last decade significant progress has been made and the problem was reduced by using alcoholic and polar solvents.…”

(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis-[diphenylphosphine](Xantphos)

“…50, 51 The synthesis of secondary and tertiary aliphatic amines takes place by Rh-Xantphos or Rh-Iphoscatalyzed chemo-and regioselective hydroaminomethylation of short and long chain α-olefins. 52, 53 Using a most suitable Pd-Xantphos catalyst, the hydroamination of vinylarenes and dienes with arylamines occurs selectively in the presence of potentially reactive functional groups. 54 Moreover, the Pd-Xantphos catalyzed hydroamination can be used for the sequential formation of tropene derivatives, starting with cycloheptatriene and anilines.…”

Hydroaminomethylation of Natural Allylic and Homoallylic Alcohols: A Ligand‐Controlled Route to New Amines

“…Although HAM has been described for a long time, only recently with the important contributions from Eilbracht [16] and Beller [17–19] groups this reaction has gained importance for the synthesis of complex molecules with biological potential and consequent applications in the pharmaceutical industry. The use of phosphine or phosphite ligands allows to control the reaction selectivity and, in some cases, improve catalytic activity [20] .…”