Amine hydrochloride salts as bifunctional reagents for the radical aminochlorination of maleimides

Abstract

Amine hydrochloride salts have been typically used as amination reagents. Contrary to conventional use, HCl is released as waste residue. Herein, we disclose a new utilization of amine hydrochloride as...

Copper‐Catalyzed Oxidative Carboamination of Maleimides with Amines and α‐Bromo Carboxylates

“…In addition, the addition of one equivalent CuBr 2 into the reaction of 1 a and 2 a did not produce bromoaminated maleimide (eq. 5), which indicated that the present reaction mechanism was completely different from the previously found mechanism [5b,c] . In addition, when 3 a and 5 a were stirred under optimal reaction conditions, the alkylation product 4 a was obtained (eq.…”

Unprecedented Route to Amide-Functionalized Double-Decker Silsesquioxanes Using Carboxylic Acid Derivatives and a Hydrochloride Salt of Aminopropyl-DDSQ

“…56 To confirm whether this molecular packing motif is present in the solid, powder X-ray diffraction (PXRD) was measured. It turns out that the diffraction peaks in the calculated pattern, 57 based on the crystal structure, coincide with the measured one (Figure 4A, B). This can prove the presence of channels for the polycrystalline form, suggesting the potential use of 2 as a sorbent material.…”

“…Moreover, according to our best knowledge, we present for the first time a method for the synthesis of DDSQ amine hydrochloride salt, which has better stability than the amine derivative. Their interesting reactivity can be used in some specific functionalization methods, which are unapproachable for amine groups, i.e., aminochlorination of maleimides, 57 amide synthesis using aldehydes, 58 ring-opening polymerization, 59 , 60 Mannich reaction, 61 Chichibabin pyridine synthesis, 62 4-amino imidazole synthesis, 63 or the synthesis of pyrrolin-4-ones. 64 …”

Aminohalogenation of maleimides with alkylamines and XCH2CH2X (X = Cl, Br)

“…Remarkably, the catalytic amount of HI promoted the unexpected radical aminochlorination of maleimides. Beyond a common solvent, the use of cheap 1,2-dihaloethane as a halogenated reagent could complement the limitation of HCl, and conventional electrophilic halogenation reagents such as NXS (X = Cl, Br) [12] enabled the previously unreachable electrondeficient alkenes twofold aminochlorination and oxidative aminobromination. The current strategy not only reduces the waste of halogen salt but also broadens the application range of 1,2-dihaloethane.…”