Visible-Light-Promoted Metal-Free Approach for the N-H Insertions by Using Donor/Donor Diazo Precursors

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Zhang, Yu ; Li, Qiannan ; Wang, Jinxin ; Lin, Jingchuan ; Xia, Dingding ; Wang, Ping ; Luan, Xin ; Das, Shoubhik ; Zhang, Wei-Dong ; Hao, Er-Jun:
Visible-Light-Promoted Metal-Free Approach for the N-H Insertions by Using Donor/Donor Diazo Precursors.
In: Green Chemistry. Bd. 26 (2024) Heft 8 . - S. 4600-4608.
ISSN 1463-9262
DOI der Verlagsversion: https://doi.org/10.1039/D3GC04431A

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Abstract

The metal-catalyzed carbenoid-based N-H insertions of α-stabilized diazo compounds and relative precursors serve as a robust strategy for the formation of C-N bonds. However, carbenoid-based N-H insertions with aminopyridines are usually incompatible due to the undesired coordination effect between the pyridine and the metal. Moreover, coupling of donor/donor diazo compounds with amines still remains challenging due to the instability and unavailability of donor/donor diazo compounds. Considering all these existing challenges, herein, a metal-free strategy is reported to achieve N-H insertions via coupling donor/donor diazo precursors (N-tosylhydrazones) with a plethora of amines including aminopyridines, anilines, aliphatic amines, and other nucleophiles such as imidazoles, pyrroles, and indoles. Expediently, β-amino esters are also afforded by using this mild strategy. The utility of this protocol is further demonstrated by the gram-scale synthesis and modifications of pharmaceuticals. Therefore, it’s very clear that this metal-free approach uniquely tolerates a wide range of nucleophiles and that opens a straightforward synthetic route to synthesize diverse value-added amines.