123567-61-3Relevant academic research and scientific papers
Efficient α-Alkylation of Arylacetonitriles with Secondary Alcohols Catalyzed by a Phosphine-Free Air-Stable Iridium(III) Complex
Panda, Surajit,Saha, Ratnakar,Sethi, Subrat,Ghosh, Rahul,Bagh, Bidraha
, p. 15610 - 15621 (2020/12/01)
A well-defined and readily available air-stable dimeric iridium(III) complex catalyzed α-alkylation of arylacetonitriles using secondary alcohols with the liberation of water as the only byproduct is reported. The α-alkylations were efficiently performed at 120 °C under solvent-free conditions with very low (0.1-0.01 mol %) catalyst loading. Various secondary alcohols including cyclic and acyclic alcohols and a wide variety of arylacetonitriles bearing different functional groups were converted into the corresponding α-alkylated products in good yields. Mechanistic study revealed that the reaction proceeds via alcohol activation by metal-ligand cooperation with the formation of reactive iridium-hydride species.
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.
