On the way to the perfect reaction: Efficient synthesis of linear amines and alcohols from olefinic mixtures

ORGN 29

Matthias Beller, Institut für Organische Katalyseforschung an der Universität Rostock e.V, Buchbinderstr. 5-6, Rostock, 18055, Germany
The direct synthesis of linear aliphatic alcohols and amines via anti-Markovnikov reaction of terminal olefins with N- or O-nucleophiles is viewed as one of the most important goals for catalysis. Even more challenging is the synthesis of the linear functionalized products from internal olefins. Such processes are of significant value to the chemical industry because mixtures of internal aliphatic olefins such as butenes, and octenes are significantly cheaper compared to the pure terminal isomers. Recently, we have developed the first selective hydroaminomethylation reaction of internal olefins to linear amines. This clean four-step one-pot process for aliphatic amines utilizes the most economically attractive and readily available feedstock. In this contribution we present second-generation catalysts, which show significantly higher rate and allow for the first time for the hydroaminomethylation of mixtures of functionalized olefins. In addition, the first functionalization reactions of olefinic mixtures in biphasic mixtures will be presented, which show unprecedented selectivity towards the desired linear isomers.