000001874 001__ 1874 000001874 005__ 20251007025126.0 000001874 0247_ $$2doi$$a10.6082/uchicago.1874 000001874 037__ $$aTHESIS$$bDissertation 000001874 041__ $$aeng 000001874 245__ $$aRhodium-Catalyzed C−C Bond Activation of Four-Membered Ring Ketones 000001874 260__ $$bUniversity of Chicago 000001874 269__ $$a2019-06 000001874 300__ $$a529 000001874 336__ $$aDissertation 000001874 502__ $$bPh.D. 000001874 520__ $$aTransition 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. 000001874 540__ $$a© 2019 Lin Deng 000001874 650__ $$aOrganic chemistry 000001874 653__ $$aC−C Bond 000001874 653__ $$aCut-and-Sew 000001874 653__ $$aKetone 000001874 653__ $$aRhodium 000001874 690__ $$aPhysical Sciences Division 000001874 691__ $$aChemistry 000001874 7001_ $$aDeng, Lin$$uUniversity of Chicago 000001874 72012 $$aGuangbin Dong 000001874 72014 $$aViresh Rawal 000001874 72014 $$aScott Snyder 000001874 8564_ $$959b6ffda-a113-48f7-9e93-7b841ac887b9$$eEmbargo (2019-12-24)$$s54751172$$uhttps://knowledge.uchicago.edu/record/1874/files/Deng_uchicago_0330D_14823.pdf 000001874 909CO $$ooai:uchicago.tind.io:1874$$pDissertations$$pGLOBAL_SET 000001874 983__ $$aDissertation