Closer Investigation of the Kinetics and Mechanism of Spirovinylcyclopropyl Oxindole Reaction with 3Σ-g-O2 by Topological Approaches and Unraveling the Role of the I2 Catalyst.

In this investigation at the MN15L/Def2-TZVP level of theory, we present computational evidence indicating that the reaction of 3Σ-g-O2 with spirovinylcyclopropyl oxindole (2) leads to a product called spiro-1,2-dioxolane (2) in its singlet state; this reaction occurs via a stepwise mechanism and its rate-determining step is catalyzed by iodine radicals, which promotes opening of the three-membered ring under dark conditions. The conversion of 2 to 1-benzylindoline-2,3-dione (3) and 2-vinyloxirane (4) takes place via a concerted and slightly asynchronous reaction. Both electron localization function and AIM topological analysis reveal that the step associated with the attack of the 3Σ-g-O2 molecule on the intermediate 3MC characterizes the formation of the only new O2-C3 single bond, which occurs in a stepwise mechanism, in contrast to the Δg-O2 reaction with 15 species.