Synthesizing Complex Quaternary Carbons by the Sequence-Regulated Additions of tert -Alkyl Radicals to Two Different Olefins.

We report the sequence-regulated radical additions of tert -alkyl radicals to two different olefins controlled by a Cu catalyst, which we term the "atom-transfer radical addition-substitution" reaction. The reactions of α-bromocarbonyl compounds, such as tert -alkyl radical sources, with methacrylates and styrenes occur in a sequence-regulated manner to give the corresponding three-component product possessing skipped quaternary carbon centers. Our method provides new insight into how to control the reactivities of tert -alkyl radicals during the synthesis of regulated aliphatic chains.