Palladium-catalysed anti-Markovnikov selective oxidative amination.

Autor: Kohler DG; Department of Chemistry, University of Illinois, Urbana-Champaign, 600 S. Mathews, Urbana, Illinois 61801, USA., Gockel SN; Department of Chemistry, University of Illinois, Urbana-Champaign, 600 S. Mathews, Urbana, Illinois 61801, USA., Kennemur JL; Department of Chemistry, University of Illinois, Urbana-Champaign, 600 S. Mathews, Urbana, Illinois 61801, USA., Waller PJ; Department of Chemistry, University of Illinois, Urbana-Champaign, 600 S. Mathews, Urbana, Illinois 61801, USA., Hull KL; Department of Chemistry, University of Illinois, Urbana-Champaign, 600 S. Mathews, Urbana, Illinois 61801, USA.
Jazyk: angličtina
Zdroj: Nature chemistry [Nat Chem] 2018 Mar; Vol. 10 (3), pp. 333-340. Date of Electronic Publication: 2018 Jan 01.
DOI: 10.1038/nchem.2904
Abstrakt: In recent years, the synthesis of amines and other nitrogen-containing motifs has been a major area of research in organic chemistry because they are 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 a 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 palladium-catalysed oxidative amination reaction in which 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 through trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favoured products. Both the scope of the transformation and mechanistic investigations are reported.
Databáze: MEDLINE
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