Transition metal-catalyzed C−C σ-bond cleavage of cyclic compounds followed by 2π-insertion, namely a “cut-and-sew” approach, has recently emerged as an attractive approach for complex bridged or fused ring formation. Comparing with traditional approaches, these methods operate at near pH and redox neutral conditions, and usually in a highly atom-economical manner. In this thesis, introduction of the history and recent advancement in the field was provided. Based on the current limitations of this approach, we designed and realized the enantioselective carboacylation of C=N bonds and C=C bonds through C−C activation of benzocyclobutenones and applied this new approach to the asymmetric total synthesis of (−)-cycloclavine. In addition, the racemic and enantioselective "cut-and-sew" reactions between the alkynes or olefins and the alfa-branched cyclobutanones were developed.