1664-39-7Relevant articles and documents
Transition metal-free methylation of amines with formaldehyde as the reductant and methyl source
Man, Nikki Y.T.,Li, Wanfang,Stewart, Scott G.,Wu, Xiao-Feng
, p. 345 - 347 (2015/11/25)
A simple transition metal-free procedure using formaldehyde for the N,N-dimethylation and N-methylation of primary and secondary anilines is reported. The reaction showed limitations on sterically hindered and electron-withdrawing anilines, but is successful on amines with electron-donating substituents. Formaldehyde acts as both the reducing agent and the carbon source in the reaction.
Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen or hydrogen peroxide and sodium cyanide: Sp3 C-H bond activation and carbon-carbon bond formation
Murahashi, Shun-Ichi,Nakae, Takahiro,Terai, Hiroyuki,Komiya, Naruyoshi
supporting information; experimental part, p. 11005 - 11012 (2009/02/05)
Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen in the presence of sodium cyanide and acetic acid gives the corresponding α-aminonitriles, which are highly useful intermediates for organic synthesis. The reaction is the first demonstration of direct sp3 C-H bond activation α to nitrogen followed by carbon-carbon bond formation under aerobic oxidation conditions. The catalytic oxidation seems to proceed by (i) α-C-H activation of tertiary amines by the ruthenium catalyst to give an iminium ion/ruthenium hydride intermediate, (ii) reaction with molecular oxygen to give an iminium ion/ruthenium hydroperoxide, (iii) reaction with HCN to give the α-aminonitrile product, H2O2, and Ru species, (iv) generation of oxoruthenium species from the reaction of Ru species with H2O2, and (v) reaction of oxoruthenium species with tertiary amines to give α-aminonitriles. On the basis of the last two pathways, a new type of ruthenium-catalyzed oxidative cyanation of tertiary amines with H2O2 to give α-aminonitriles was established. The α-aminonitriles thus obtained can be readily converted to α-amino acids, diamines, and various nitrogen-containing heterocyclic compounds.
Conformation-Dependent Intramolecular Electron Transfer in N-(Aminoalkyl)-9-phenanthrenecarboxamides
Lewis, Frederick D.,Burch, Erick L.
, p. 4055 - 4063 (2007/10/03)
The molecular structure and photophysical behavior of several secondary and tertiary N-(aminoalkyl)phenanthrenecarboxamides have been investigated.Secondary (aminoalkyl)amides exist predominantly in the Z conformation, whereas tertiary amides exist as mixtures of Z and E conformers and semirigid piperazines as mixtures of chair conformers.Rate constants for endergonic intramolecular electron transfer are found to be highly dependent upon molecular structure.The aromatic and amide groups of the tertiary amides are essentially orthogonal, and thus, an E aminoalkyl group can adopt low-energy conformations in which there is spatial overlap between the aromatic and amine groups, whereas such overlap is not possible for either a Z aminoalkyl group or the piperazines.The observation of more rapid intramolecular electron transfer quenching of the phenanthrene singlet by an appended trialkylamine in the E vs Z conformation is attributed to this difference in overlap.An increase in the phenanthrene-amide dihedral angle is also found to result in a decrease in the rate constant for intramolecular electron transfer quenching by a Z aminoalkyl group.In the case of appended tertiary anilines, efficient electron transfer quenching occurs for both Z and E conformers.The Z conformers form fluorescent exciplexes, providing a new example of exciplex-type emission in the absence of direct ?-? overlap.Exciplexes formed by the E conformers are nonfluorescent and apparently undergo rapid intersystem crossing.The strong exciplex emission observed at low temperatures both in solution and in frozen glasses is attributed to ground state dimers or aggregates.
