Synthesis of Bicyclo[n.1.0]alkanes by a Cobalt‐Catalyzed Multiple C(sp3)−H Activation Strategy

A cobalt‐catalyzed dual C(sp3)−H activation strategy has been developed and it provides a novel strategy for the synthesis of bicyclo[4.1.0]heptanes and bicyclo[3.1.0]hexanes. A key to the success of this reaction is the conformation‐induced methylene C(sp3)−H activation of the resulting cobaltabicyclo[4.n.1] intermediate. In addition, the synthesis of bicyclo[3.1.0]hexane from pivalamide, by a triple C(sp3)−H activation, has also been demonstrated. Double the activation: Described is a cobalt‐catalyzed dual C(sp3)−H activation strategy for the synthesis of bicyclo[4.1.0]heptanes and bicyclo[3.1.0]hexanes. A key to the success of this reaction is the conformation‐induced C(sp3)−H activation of the resulting cobaltabicyclo[4.n.1] intermediate. Also, the synthesis of bicyclo[3.1.0]hexane from pivalamide by triple C(sp3)−H activation is demonstrated. Q=quinolin‐8‐yl.