Intermolecular amination of allenes via twofold photocatalytic nitrene transfer reactions

28 February 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

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.

Keywords

Photocatalysis
Nitrene
Amination
Computational Chemistry
Allene

Supplementary materials

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Experimental Supplemental Information
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Supplemental Information with experimental and mechanistic data
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Computational Supplemental Information
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Energies, 3D structures and Cartesian Coordinates
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