A versatile titanocene-catalyzed radical allyl transfer reaction on epoxides is reported. Epoxide opening occurs regioselectively at the more hindered side, and variously substituted allyl sulfone may be coupled to this position in an efficient manner, enabling a rapid access to quaternary carbon centers with useful functionalities for further elaboration. Furthermore, the procedure can be expanded to stereoselective variants. This new radical allyl transfer expands the scope of allylation in organic synthesis.
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