Autocatalytic Radical Ring Opening ofN-Cyclopropyl-N-phenylamines Under Aerobic Conditions − Exclusive Formation of the Unknown Oxygen Adducts,N-(1,2-Dioxolan-3-yl)-N-phenylamines

Ring-opening, cycloaddition and rearrangement reactions of nitrogen-substituted cyclopropane derivatives

“…It is worthy of note that the method is also applicable to alkyne substrates (entry 5). Although it is clear that oxygen alone performs poorly in the oxidation of aminocyclopropanes, as also evidenced by earlier studies, 16 using tris(1,10-phenphenanthroline)iron(III) hexafluorophosphate (Scheme 27). 16 Other oxidising systems were investigated and found to be suitable: benzoyl peroxide in the dark at −20 °C or tert-butyl peroxide under UV irradiation at room temperature.…”

Synthesis of Cyclic Peroxides

“…In particular instances, the incipient carbon-centered radical is obtained in an all-homolytic autoxidation process. For example, autoxidation of carota-1,4-dien-14-al (197) afforded the bridged tricyclic peroxide-hydroperoxide 198 in 57% yield (Scheme 45) 192 -194 . The radical chain mechanism is initiated by a spontaneous hydrogen atom abstraction from substrate 197 to …”

“…process including an oxidative ring opening of the cyclopropane ring 197 . Pentasubstituted 3-hydroxy-1,2-dioxolanes 215 were obtained in moderate yields through homolysis of α-azohydroperoxides 214 under pure oxygen, probably by the mechanism described in Scheme 49 198,199 .…”

Titanium-mediated syntheses of cyclopropylamines

“…For example, a large variety of N -cyclopropyl-N -arylamines of type 70 and their isotopically labeled analogues have been prepared from the corresponding formamides for mechanistic studies of Cytochrome P450-catalyzed N -dealkylations and autocatalytic radical ring-opening reactions under aerobic conditions [99][100][101].…”