Development of Greener Catalytic Synthetic Methods of Nitrogen-Containing Compounds Using N-Unprotected Ketimines

2022 ◽  
Vol 80 (1) ◽  
pp. 2-13
Author(s):  
Hiroyuki Morimoto
Author(s):  
A. R. Nallayagari ◽  
E. Sgreccia ◽  
R. Pizzoferrato ◽  
M. Cabibbo ◽  
S. Kaciulis ◽  
...  

AbstractCarbon quantum dots (CQD) were prepared from three different precursors and by three bottom-up synthesis methods: classical pyrolysis of citric acid (CAP), microwave irradiation of glucose (GM), and hydrothermal treatment of glucosamine hydrochloride (GAH). CQD were further functionalized using various nitrogen-containing compounds: 6-aminohexanoic acid, 1,6-diaminohexane, N-octylamine, dimethylamine, and tryptophan. Special attention was dedicated to investigate how the combination of synthetic method and starting material affected the nature and properties of CQD. The analysis indicated that CAP were good candidates for covalent post-functionalization, GM allowed an easy passivation, and GAH permitted the direct introduction of nitrogen into the core. The size distribution showed a core–shell structure for CQD functionalized with an aminoacid by microwave irradiation, whereas the thermal decomposition evidenced the degradation of functionalizing molecules and the presence of pyridinic and pyrrolic nitrogen after hydrothermal synthesis. Photoluminescence spectra revealed important differences between the synthesis techniques, related to the occurrence of surface states, and the highest fluorescence quantum yield for hydrothermally prepared CQD. These approaches led to CQD with properties that can be exploited in many fields from energy conversion to sensing.


Author(s):  
X.-L. Lu ◽  
B. Wang ◽  
S. Chiba

AbstractNitrogen-containing compounds are prevalent in the key components of various functional materials and compounds such as pharmaceutical drugs. Therefore, it is extremely important to develop versatile synthetic methodologies capable of constructing C—N bonds in an efficient manner under milder reaction conditions. Apart from common ionic C—N bond-forming reactions (i.e., nucleophilic and electrophilic amination, as well as transition-metal-catalyzed C—N cross-coupling processes), leveraging of nitrogen-centered radicals for C—N bond-forming process has created another dimension to the modern synthesis of nitrogen-containing compounds. In particular, recent development of novel catalytic strategies and the design of new nitrogen-radical precursors have rendered their generation and use for C—N bond formation more practical and user-friendly for synthesis of wider array of nitrogen-containing compounds of potential use. This chapter highlights the latest developments in synthetic methods for C—N bond construction using nitrogen-centered radicals by showing selected reactions, mostly reported in the last five years, based on their structural and reactivity features as well as the method of radical generation.


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