Radical-Mediated α- tert -Alkylation of Aldehydes by Consecutive 1,4- and 1,3-(Benzo)thiazolyl Migrations.

The direct alkylation of the α-position of aldehydes is an effective method for accessing a wide range of structurally diverse aldehydes, yet tert -alkylation has proven to be a challenging task. In this study, we present a novel radical-mediated tert -alkylation approach targeting the α-position of aldehydes, enabling the synthesis of complex aliphatic aldehydes. The transformation is initiated by the interaction between an in situ generated enamine intermediate and α-bromo sulfone, forming an electron donor-acceptor (EDA) complex, followed by consecutive 1,4- and 1,3-functional group migrations. This protocol operates under metal-free and mild photochemical conditions, delivering a broad scope of products and providing new mechanistic insights into radical rearrangement reactions.