2-Silyloxyfurans Go Radical: Photochemical Access to γ-Functionalized Butenolides

2-Silyloxyfurans, one of the most exploited heterocyclic nucleophiles in vinylogous polar processes, are herein unlocked as versatile platforms in radical-mediated, vinylogous transformations. We have developed a set of photopromoted strategies which unveiled a dual, complementary reactivity of 2-Silyloxyfurans: i. as electron-rich dienes capable to intercept electrophilic α-ketoradicals or suitable benzyl carbocations selectively at the γ-position; and ii. as precursors of easily accessible silyl radical cation intermediates capable of engaging a radical-radical coupling with nucleophilic, open shell intermediates. These pathways provide direct γ-functionalization of the butenolide core, delivering structurally diverse chiral products in one step, namely ε-ketobutenolides and γ-benzylbutenolides.