Nickel-Catalyzed Strain-Release Alkyl–Alkyl Cross-Coupling of N -Chlorocyclopropamides with Tertiary α-Bromo Esters

Abstract We report a nickel-catalyzed alkyl–alkyl cross-electrophile coupling of N-chlorocyclopropamides with tertiary alkyl bromides. This method leverages cyclopropane strain release to generate alkyl radicals via β-scission of nitrogen-centered radicals, enabling efficient C(sp3)–C(sp3) bond formation under mild reductive conditions. The protocol exhibits a broad substrate scope and excellent functional-group tolerance, affording diverse aliphatic products in good to excellent yields. Mechanistic studies support a radical relay pathway driven by strain-release ring opening and nickel-mediated cross-coupling. This strategy provides a modular, practical approach to complex aliphatic frameworks, expanding the utility of strain-release chemistry in cross-electrophile coupling.