Allene Aziridination as a Tool for the Synthesis of Complex Amines

Liu, Lu; Schomaker, Jennifer M.

doi:10.1016/b978-0-12-811651-7.00006-6

Cited by 1 publication

(1 citation statement)

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“…8,12 These catalysts however prove inefficient in a generalized amination reaction of allenes and current methods remain strictly limited (Figure 1a). 13,14 The only high-yielding approach lies within the development of intramolecular, oxidative amination reactions as demonstrated independently by the Blakey, 15,16 Robertson, 17 and Schomaker 18-21 groups using Rh(II) or Ag(I) catalysts (Figure 1b). The intermolecular nitrene transfer reaction with allenes is however much more challenging.…”

Section: Introductionmentioning

confidence: 99%

Intermolecular amination of allenes via twofold photocatalytic nitrene transfer reactions

Guo

Empel

Pei

et al. 2022

Preprint

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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.

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