Additive-Free Pd-Catalyzed α-Allylation of Imine-Containing Heterocycles

Marko Kljajic; Johannes G Puschnig; Hansjörg Weber; Rolf Breinbauer

doi:10.1021/acs.orglett.6b03407

Additive-Free Pd-Catalyzed α-Allylation of Imine-Containing Heterocycles

Org Lett. 2017 Jan 6;19(1):126-129. doi: 10.1021/acs.orglett.6b03407. Epub 2016 Dec 12.

Authors

Marko Kljajic¹, Johannes G Puschnig¹, Hansjörg Weber¹, Rolf Breinbauer¹

Affiliation

¹ Institute of Organic Chemistry, Graz University of Technology , Stremayrgasse 9, A-8010 Graz, Austria.

Abstract

An additive-free Pd-catalyzed α-allylation of different imino-group-ontaining heterocycles is reported. The activation of α-CH pronucleophiles (pK_a (DMSO) > 25) occurs without the addition of strong bases or Lewis acids using only the Pd/Xantphos catalyst system. The reaction scope has been studied for various 5- and 6-membered nitrogen-containing heterocycles (yields up to 96%). Mechanistic investigations suggest an initial allylation of the imine-N followed by a Pd-catalyzed formal aza-Claisen rearrangement.

Publication types

Research Support, Non-U.S. Gov't