Factors Influencing the Course and Mechanism of Grignard Reactions. XV. The Reaction of β,β-Dimethylphenethyl Chloride with Phenylmagnesium Bromide in the Presence of Cobaltous Chloride

Exceptionally high decarboxylation rate of a primary aliphatic acyloxy radical determined by radical product yield analysis and quantitative 1H‐CIDNP spectroscopy

“…Diphenylbutane and 2‐cyclopentylethanol (Alfa Aesar, both 97%) were used as received; ethylbenzene, vinylcyclopentane (99%), 3‐cyclopentylpropanoic acid (98%), 3‐phenylpropanoic acid (99%), and ethylcyclopentane (99%) were obtained from Aldrich and used without further purification. m ‐CPBA was recrystallized from aqueous pH 7.4 phosphate buffer 44. The procedures for the GC, GC/MS, and 1 H‐NMR analysis of peroxide decomposition product yields were reported previously 10, 11…”

Free-Radical Rearrangements

“…Urry and Kharasch's (5) pioneering discovery of the neophyl rear rangement, QH 5 C(CH 3 ) 2 CH 2 -*-QH 5 CH 2 C(CH 3 ) 2 1 2…”

“…The ultimate in electron deficiency is achieved by protonation of the nitrogen. Yields of cyclized product are generally over 80% and, although 1,5-migration is favored, 1,6-migration can occur (just as is the case with alkoxy radicals), e.g., R(CH 2 ) 5 However, from a synthetic viewpoint, probably their most important reaction is the intramolecular 1,5-hydrogen migration-the well-known Hoffmann-Löffler reaction, 366 -> 367 (4, 286a, 596, 597).…”

BF3⋅OEt2‐Catalyzed Intermolecular Reactions of Vinylidenecyclopropanes with Bis(p‐alkoxyphenyl)methanols: A Novel Cationic 1,4‐Aryl‐Migration Process

“…Regarding aryl migration, [6] besides the most extensively investigated 1,2-aryl migration (neophyl rearrangement), [7] 1,4-aryl-migration reactions have been also observed and studied. It has been known that this migration can take place between two carbon atoms, or between a carbon atom and a heteroatom, as well as between two heteroatoms.…”