The development of efficient methods for C(sp³)–C(sp³) bond formation remains a longstanding challenge in synthetic chemistry, especially in palladium catalysis employing sterically bulky electrophiles. In this study, we present a novel approach for achieving C(sp³)–C(sp³) cross-coupling via photoinduced palladium catalysis, employing cyclopropanols as masked C(sp³)-nucleophiles. Leveraging the unique reactivity of photoexcited palladium, this protocol enables radical-mediated C(sp³)–C(sp³) coupling across a broad range of substrates including sterically hindered and functionally diverse alkyl halides under mild conditions. This method significantly expands the extent of palladium-catalysed cross-coupling for bond construction between sp³-hybridized carbon units, providing streamlined access to structurally complex C(sp³)-rich frameworks that are crucial for medicinal chemistry.

https://doi.org/10.1039/d5sc02325d