Catalytic intermolecular linear allylic C-H amination via heterobimetallic catalysis.

Nitrogen functionality is prevalent in synthetic and natural small molecules with significant biological activities.1 Current state-ofthe-art methods for installing nitrogen into complex organic frameworks generally proceed through oxygen.2 While these methods feature high selectivities and predictable reactivities, they lengthen synthetic sequences by requiring unproductive chemical manipulations to install and maintain oxygen functionality. Reactions that selectively convert C-H directly to C-N stand to significantly streamline synthetic sequences by providing obvious disconnections that avoid handling oxidized materials.3 While significant advances have been made in developing preparatively useful intramolecular C-H aminations,4a,5 catalytic intermolecular C-H aminations are scarce and often require excess substrate.6,7 We report herein the first general, catalytic, intermolecular allylic C-H amination reaction. This reaction directly converts a wide range of R-olefins to linear (E)-allylic amines with good yields and outstanding regioand stereoselectivities (>20:1) using limiting amounts of the starting olefin. Critical for achieving this catalytic reactivity is a heterobimetallic system composed of Pd/bis-sulfoxide and Cr(salen) catalysts.