Abstract
Transition-metal-free transformations are recognized as green and sustainable methods for constructing carbon-carbon bonds in organic synthesis. This review describes the application of six organic peroxides, including tert-butyl hydroperoxide (TBHP), di-tert-butyl peroxide (DTBP), tert-butyl peroxybenzoate (TBPB), benzoyl peroxide (BPO), dialauroyl peroxide (DLP), and diguyl peroxide (DCP), in C-C bond construction, highlighting selected examples and mechanisms of challenging transformations. Each section concludes with a detailed overview of suitable reagents for various coupling reactions and strengths and weaknesses of the reported works. This work aims to inspire further innovations in transition-metal-free oxidative transformations, promoting sustainable and eco-friendly chemical processes and paving the way for new peroxide-based organic synthesis methods.