The incorporation of difluoromethylene (CF₂) group into chemical molecules often imparts desirable properties such as lipophilicity, binding affinity, and thermal stability. Consequently, the increasing demand for gem-difluoroalkylated compounds in drug discovery and materials science has continued to drive the development of practical methods for their synthesis. However, traditional synthetic methods such as deoxofluorination often confront challenges including complicated substrate synthesis sequences and poor functional group compatibility. In this context, we herein report a metal electron-shuttle catalyzed, modular synthetic methodology for difluoroalkylated compounds by assembling two C(sp³) fragments across CF₂ unit in a single step. The approach harnesses a difluoromethylene synthon as a biradical linchpin, achieving the construction of two C(sp³)-CF₂ bonds through radical addition to two different π-unsaturated molecules. This catalytic protocol is compatible with broad range of coupling partners including diverse olefins, iminiums, and hydrazones, supporting endeavors in the efficient construction of C(sp³)-rich difluoroalkylated molecules.

将二氟亚甲基 (CF ₂ ) 基团掺入化学分子中通常会赋予所需的特性，例如亲脂性、结合亲和力和热稳定性。因此，药物发现和材料科学中对偕二氟烷基化化合物的需求不断增长，继续推动其合成实用方法的发展。然而，脱氧氟化等传统合成方法常常面临底物合成序列复杂、官能团兼容性差等挑战。在此背景下，我们在此报告了一种金属电子穿梭催化的二氟烷基化化合物的模块化合成方法，通过一步在CF ₂单元上组装两个C(sp ³ )片段。该方法利用二氟亚甲基合成子作为双自由基关键，通过对两个不同的π不饱和分子进行自由基加成来构建两个C(sp ³ )-CF ₂键。该催化方案与广泛的偶联伙伴兼容，包括不同的烯烃、亚胺和腙，支持高效构建富含 C(sp ³ ) 的二氟烷基化分子。