Abstract
<title>Abstract</title> <p>Homologation plays a critical role in pharmaceuticals, natural products, agrochemicals, and petroleum products due to its capacity to insert carbon-based units and precisely control carbon chain growth. However, compared to homologation of other polar func-tional groups, the homologation of electron-deficient alkenes，particularly direct and controllable carbon-increasing homologation remains challenging. Here, we report a photoinduced strategy to selectively achieve tunable carbon-increasing homologation of electron-deficient alkenes with cycloalkyl hydroperoxides as carbon-based units. This process encompasses oxygen radical-mediated C–C bond cleavage, followed by in situ Giese-type addition, and a second C–C bond scission mediated by the Norrish type II reaction. The approach is demonstrated broad substrate scope (such as mono-, 1,1-di, 1,2-di and 1,2,3-trisubstituted olefins) and excellent functional group compatibility (such as cyano, free carboxylic acids, primary amines, and alcohols). Moreover, this protocol provides direct tunable (CH2)n (n = 1-8…) insertion without multi-step iterative reactions, only by adjusting the size of the ring of the cycloalkyl hydroperoxides.</p>