Strategic design for the construction of contiguous tetrasubstituted carbons represents a daunting challenge in synthetic organic chemistry. Herein, we report a combined experimental and computational investigation aimed at developing catalytic aerobic carbooxygenation, involving the intramolecular addition of tertiary radicals to geminally di-substituted-alkenes followed by aerobic oxygenation. This reaction provides astraightforward route to various α,α,β,β-tetrasubstituted γ-lactones, which can be readily transformed into hexasubstituted γ-lactones through allylation/translactonization. Computational analysis reveals that the key mechanistic foundation for achieving the developed aerobic carbooxygenation involves the design of endothermic (energetically uphill) C-C bond formation followed by exothermic (energetically downhill) oxygenation. Furthermore, we highlight a unique fluorine- induced stereoelectronic effect that stabilizes the endothermic stereo-determining transition state.