Abstract
The amination with monovalent, nitrogen-based intermediates constitutes an important reaction for the construction of valuable amines. The high basicity of reagents, reaction intermediates or products however poses significant challenges to metal-catalyzed amination through coordination and blocking of catalytically active sites and hampering their efficiency. In this context, high-yielding intermolecular amination reaction of allenes remain an unsolved challenge in organic synthesis and general methods are not available. Herein, we describe a photochemical approach towards the intermolecular amination of allenes via free nitrene radical anions as the key reactive intermediate. This reaction proceeds without the participation of catalyst-bound nitrogen species and can thus overcome current limitations. We report on the application in the amination of allenes to give azetidine and cyclopropyl amines with a broad and general substrate scope. Experimental and theoretical studies were performed to provide an understanding of the reaction mechanism and rationalize the high efficiency of this photocatalytic approach.
Content

Supplementary material

Experimental Supplemental Information
Supplemental Information with experimental and mechanistic data

Computational Supplemental Information
Energies, 3D structures and Cartesian Coordinates