The Development of Selenium Catalyzed C-H Allylic Aminations and Palladium Catalyzed Aziridine Cross Coupling

Abstract

Allylic and homoallylic amines have long been valued as key synthetic intermediates in the production of nitrogen-containing compounds due to their ease of synthesis and the presence of a readily functionalizable alkene moiety. Despite the advancements in organic methodology, synthesizing these highly valuable nitrogen containing compounds remains challenging due to limitations in current existing methods. Herein, the synthesis of homoallylic amines with highly substituted alkenes was realized using a palladium catalyst starting from alkyl aziridines and alkenylboronic acid. This reaction provides facile access to highly regioselective homoallylic amines and provides an alternative to enantiospecific synthesis with a chiral starting aziridine. A metal free direct C-H allylic amination was achieved using a selenium-based catalyst. We discovered that the ligand plays a critical role, enabling the incorporation of nitrogen functionality onto mono-, di-, tri-, and tetrasubstituted alkenes with high regioselectivity and diastereoselectivity. Biological active molecules were coupled to complex natural products demonstrating the utility of this developed reaction in late-stage functionalization.