Terpene‐Derived Highly Branched C₃₀‐Amines via Palladium‐Catalysed Telomerisation of β‐Farnesene

Abstract

The synthesis of highly branched long chain amines in one step is still a challenge. The palladium catalysed telomerisation of the renewable sesquiterpene b-farnesene with secondary amines yields such tertiary amines and thus, was investigated within this work. Preliminary, a suitable palladium catalyst system was developed by a high-throughput screening. It efficiently allows for the synthesis of tertiary amines with a highly branched C 30 -carbon chain with yields up to 94% of the corresponding desired allylic C 30 -amines. The generality of the protocol was proven for thirteen amines with linear and branched alkyl and aryl groups. A clear correlation between the scaffold of the amine, basicity and the activity as nucleophile in the telomerisation was uncovered. Based on the different polarities of the nonpolar in-situ formed C 30 -substituted tertiary amines and the polar solvent, a proof of concept for catalyst recovery by simple decantation was shown.

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

“…It is produced by yeast fermentation and has attracted attention in both academic and industrial research and development. Since the large and bulky substituent is located at the 2 nd position, the 1,3‐diene unit is prone to conversion with nucleophiles, even during telomerization with amines . This leads to highly‐branched polyunsaturated C 30 ‐amines (Scheme ).…”

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

“…By an intrinsic formation of a second phase after conducting the reaction and cooling down by an ice‐bath, a simple catalyst recovery concept was found. In a proof of concept, the catalyst phase was reused three times and the turnover number was increased from 400 to 605 …”

Neue Mitglieder der Royal Society: P. L. Arnold, M. A. Brimble, F. Caruso, R. S. Goody, R. H. Crabtree, C. Bertozzi, J. Sauer / Jochen‐Block‐Preis: A. Vorholt / Otto‐Bayer‐Preis: T. Erb

“…Vorholt und seine Gruppe interessieren sich für neue Katalysesysteme, Techniken zur Abtrennung von Produkten und Katalysatoren, Reaktordesign und kontinuierlich arbeitende Kleinanlagen für Langzeitexperimente. Chemistry—A European Journal veröffentlichte einen Bericht über die Synthese linearer Diester, und in Advanced Synthesis & Catalysis beschrieb er die Synthese hoch verzweigter langkettiger Amine …”