Based on these results, we applied our selected reaction conditions (Table ) to an open-chain substrate 4f, in a telescoped procedure where the siloxane is cleaved upon treatment with HCl. Unexpectedly, this open-chain analogue of 4a required 6 h to reach complete conversion (Table , entry 1). To improve the reaction rate, 4CzIPN was replaced by the more efficient photocatalyst [Ir(dtbbpy)(ppy)2]PF6 for further development. A solvent screening performed with 4f confirmed acetonitrile/methanol 9:1 (Table , entry 2) as the best solvent system. Next, the optimized photoredox reaction/acidic desilylation procedure was successfully applied to a wide range of substrates (Scheme 2). Although most radical group transfers produced secondary homoallylic alcohols, the procedure also proved applicable to primary (6j) and tertiary (6e) alcohols. Moreover, the protocol showed good functional group tolerance towards ketones (6r, 6v), esters (6m, 6t), amides (6u), carbamates (6d), ethers (6e, 6s), and electron-rich as well as -deficient aryl groups (6o-p).