Ball-milling-enabled nickel-catalyzed radical relayed reductive cross-coupling

Nickel -catalyzed radical relayed dicarbofunctionalizations of olefins, utilizing carbon electrophiles as coupling partners, present a powerful strategy for the streamlined construction of aliphatic structures. However, traditional solution -phase methods encounter challenges such as the need for bulk solvents, limited coupling partners, long reaction times, and air -/moisture -sensitive reagents. As an alternative strategy, ball -mill -enabled metal -catalyzed crosscoupling reactions have gained attention due to their high reactivity and atomic efficiency. While many ball -mill -enabled cross -coupling reactions are limited to single- and two -component methodologies, three -component solid-state cross -coupling reactions remain relatively scarce. In this work, we report the first, to our knowledge, ball -milling -enabled Ni-catalyzed reductive dicarbofunctionalization of alkenes. Two distinct readily available electrophiles, Csp2 and Csp3 halides, are simultaneously installed across a variety of olefins at room temperature in a highly regioselective manner withing 1.5 h. By harnessing the benefits of ball milling and radical relayed reactions, we anticipate further advancements in sustainable and efficient synthetic methodologies.