123567-59-9Relevant academic research and scientific papers
Hf(OTf)4-doped Me3SiCl-catalyzed aminomethylation of arenes with N,O-acetals: Facile approach to non-natural aromatic amino acid precursors
Sakai, Norio,Asano, Junichi,Shimano, Yuta,Konakahara, Takeo
, p. 2675 - 2678 (2007)
The authors demonstrated a Hf(OTf)4-Me3SiCl-system- catalyzed aminomethylation of an aromatic compound, such as a heterocycle or an electron-rich arene, with several new types of N,O-acetals having both a cyano group and a cyclic ami
Steric Inhibition of Synergistic Radical Stabilizing Effects
Bordwell, F. G.,Bausch, Mark J.,Cheng, Jin-Pei,Cripe, Thomas H.,Lynch, Tsuei-Yun,Mueller, Mark E.
, p. 58 - 63 (2007/10/02)
Equilibrium acidities in Me2SO for 14 α-N-morpholinyl-, 6 α-N-piperidinyl-, and 7 α-cyclohexylarylacetonitriles and the oxidation potentials of their conjugate bases have been determined.The increased pKHA values by about 2 units observed in these systems, relative to the corresponding arylacetonitriles, is ascribed to the presence of increased steric constraints in the anions.Hammett plots revealed larger ρ values than for arylacetonitriles (6-7 versus 5.5), pointing to an increased negative charge density on the benzylic carbon atoms in the anions.A plot of anion oxidation potentials, Eox(A-), versus pKHA for the α-N-morpholinylarylacetonitriles was linear with a slope near unity, showing that remote substituents for the most part have very little effect on radical stabilities.A 5 and 6 kcal/mol lowering of the BDE of the acidic C-H bond caused by replacing the cyclohexyl group in α-cyclohexylphenylacetonitrile by α-N-morpholinyl or N-piperidinyl groups, respectively, is attributed to the strong donor properties of these amino functions.The effects are only about one-third as large, however, as similar effects in R2NCH2COPh, where the steric effect of Ph is absent and a synergistic effect is believed to be operative.
