24837-78-3Relevant academic research and scientific papers
Unified Synthesis of Azepines by Visible-Light-Mediated Dearomative Ring Expansion of Aromatic N-Ylides
Mailloux, Matthew J.,Fleming, Gabrielle S.,Kumta, Shruti S.,Beeler, Aaron B.
, p. 525 - 529 (2021)
Herein, we report a unified approach to azepines by dearomative photochemical rearrangement of aromatic N-ylides. Deprotonation of quaternary aromatic salts with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or N,N,N′,N'-tetramethylquanidine (TMG) under visible light irradiation provides mono- and polycyclic azepines in yields up to 98%. This ring-expansion presents a new mode of access to functionalized azepines from N-heteroarenes using two straightforward steps and simple starting materials.
The effects of an ionic liquid on unimolecular substitution processes: The importance of the extent of transition state solvation
Keaveney, Sinead T.,White, Benjamin P.,Haines, Ronald S.,Harper, Jason B.
supporting information, p. 2572 - 2580 (2016/03/01)
The reaction of bromodiphenylmethane and 3-chloropyridine, which proceeds concurrently through both unimolecular and bimolecular mechanisms, was examined in mixtures of acetonitrile and an ionic liquid. As predicted, the bimolecular rate constant (k2) gradually increased as the amount of ionic liquid in the reaction mixture increased, as a result of a minor enthalpic cost offset by a more significant entropic benefit. Addition of an ionic liquid had a substantial effect on the unimolecular rate constant (k1) of the reaction, with at least a 5-fold rate enhancement relative to acetonitrile, which was found to be due to a significant decrease in the enthalpy of activation, partially offset by the associated decrease in the entropy of activation. This is in contrast to the effects seen previously for aliphatic carbocation formation, where the entropic cost dominated reaction outcome. This change is attributed to a lessened ionic liquid-transition state interaction, as the incipient charges in the transition state were delocalized across the neighbouring π systems. By varying the mole fraction of ionic liquid in the reaction mixture the ratio between k1and k2could be altered, highlighting the potential to use ionic liquids to control which pathway a reaction proceeds through.
S-, N-, and O-glycosyl derivatives of 2-acetamido-2-deoxy-D-glucose with hydrophobic aglycons as potential chemotherapeutic agents and N-acetyl-beta-D-glucosaminidase inhibitors.
Paul,Korytnyk
, p. 27 - 43 (2007/10/02)
S-, N-, and O-Glycosyl derivatives of 2-acetamido-2-deoxy-D-glucose with hydrophobic aglycons have been obtained as potential, plasma-membrane active agents. 2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-beta-D-glucopyranose (6) was converted into benzyl,
