Palladium-catalysed anti-Markovnikov selective oxidative amination.

Abstract

In recent years the synthesis of amines and other nitrogen containing motifs has been a major area of research in organic chemistry due to their being widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a Pd-catalyzed oxidative amination reaction, where the addition of the nitrogen occurs at the less substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide via trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favored products. Both the scope of the transformation and mechanistic investigations are reported.