Intermolecular Amidation of Unactivated sp² and sp³ C—H Bonds via Palladium‐Catalyzed Cascade C—H Activation/Nitrene Insertion.

Abstract

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Silver-catalysed direct amination of unactivated C–H bonds of functionalized molecules

“…Another effective method for approaching direct amination of sp 3 C-H bonds is to utilize nitrene insertion via transition-metal catalysis (Fig. 1b) [30][31][32][33] . Amongst these, silver complexes were first founded to promote the nitrene insertion 34,35 .…”

“…1a) [16][17][18][19][20] . Many chemists have devoted themselves to searching for practical and convenient synthetic methods for accessing such ubiquitous structural units by direct oxidative amination of C-H bonds [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] . In fact, efforts toward such a goal can be traced back to the historical Hofmann-Löffler-Freytag reaction in early 19th century and its advanced versions-the Baldwin and Doll modification and the Suárez modification [21][22][23][24][25][26][27][28][29] .…”

Palladium-Catalyzed Heterofunctionalization of C-H, C=C and C≡ C Bonds

“…Another approach is to utilize more reactive nitrenes for the reaction; this was adopted by Che et al to achieve intramolecular amination of 2-arylpyridines and aromatic oximes (Scheme 46) [88]. In this work, K 2 S 2 O 8 was used to activate primary carbamates, amides and sulfonamides towards C-N formation.…”

A facile access for the C-N bond formation by transition metal-free oxidative coupling of benzylic C-H bonds and amides

“…Particularly, the amination of Csp 3 -H bonds has led to significant results since the discovery of metal nitrenoids insertion into the C-H bonds [10][11][12][13]. Various transition-metal complexes including rhodium [14][15][16][17], ruthenium [18][19][20], palladium [21][22][23][24][25], manganese [26][27][28], silver [29,30], gold [31], copper [32][33][34][35][36][37][38][39], cobalt [40][41][42] and iron [43,44] as catalysts or mediators are essential to the success of these aliphatic C-H amination reactions. Due to the presence of transition-metal impurities in the final products and/or the costly metal catalysts, a strategy involving metal-free protocol would be an attractive approach for introducing nitrogen functional groups.…”