Ammonia surrogates in the synthesis of primary amines

Abstract

Primary amines are derivatives of ammonia in which one hydrogen atom is replaced by an alkyl or aryl group. Ammonia serves as the primary nitrogen source in amination reactions, and...

Contemporary Approaches for Amide Bond Formation

“…Despite this progress, the synthesis of amides using this approach is scarcely documented, with only a single report available [153] . In this study, the formation of an iron‐nitrene radical is proposed as the intermediate, utilizing TMS‐N 3 as a surrogate for ammonia [154] to synthesize primary amides. The reaction is believed to proceed through a radical mechanism, wherein the photodegradation of TMS‐N 3 plays a crucial role in amide formation, as depicted in Figure 30.…”

Water-promoted defluorinative synthesis of fluoroalkylated 1,5-diazapentadienes by using (NH4)2CO3 as an NH2 and NH source

“…On the basis of the abovementioned experimental observations and previous literature, 14–22 two possible reaction mechanisms for the H 2 O-promoted and (NH 4 ) 2 CO 3 -enabled deiodoamination-defluoroiminization cascade of perfluoroalkyl alkenes is proposed in Scheme 3. Initially, perfluoroalkyl alkene 1 readily undergoes S N V-type C(sp 2 )–I bond displacement with a molecule of NH 3 to generate enamine B .…”

“…7,8 (2) The use of the commercially available, inexpensive, and low-toxic inorganic salt (NH 4 ) 2 CO 3 as a N -nucleophile is attractive, offering a safer and more sustainable alternative while maintaining operational simplicity even under ambient conditions. 19 (3) The requirements of multistep manufacturing, distillation for purification, harsh reaction conditions, and moisture exclusion, as well as low efficiency involved in previous methods are all circumvented. The transition-metal-free process is also advantageous, given that many existing methods rely on air- and moisture-sensitive, stoichiometric, or toxic metal additives/reagents (such as AlCl 3 , ZnCl 2 ·OEt 2 , and organometallic reagents).…”

Synthesis of Phenol–Pyridinium Salts Enabled by Tandem Electron Donor–Acceptor Complexation and Iridium Photocatalysis

“…N -Functionalized pyridinium salts can engage in rich one-electron chemistries via photoredox and electrochemical catalysis to transfer functional groups via heterolytic ( N -pyridyl radicals) or homolytic (generating C, N, or O radicals) cleavage (Figure ). − For example, Musacchio and co-workers recently implemented a photoreduction of N -alkoxy pyridinium salts as a means to generate alkoxyl radicals that are hydrogen atom transfer (HAT) reagents for benzylic amination . Watson and co-workers pioneered N -alkyl 2,4,6-triphenylpyridinium (Katritzky) salts to derivatize alkyl amines via pyridinium C–N bond cleavage …”