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Palladium-Catalyzed Regioselective and Stereospecific Ring-Opening Cross-Coupling of Aziridines: Experimental and Computational Studies

Youhei Takeda, W. M. C. Sameera, Satoshi Minakata

2020Accounts of Chemical Research90 citationsDOIOpen Access PDF

Abstract

systems). Computational studies rationalized the detailed mechanisms of the full catalytic cycle and the regioselectivity and stereospecificity of the reactions. The computational results suggested that the interactions operating between the Pd catalyst and aziridine substrate play important roles in determining the regioselection of the aziridine ring-opening event (i.e., oxidative addition). Also, the computational results rationalized the role of water molecules in promoting the transmetalation step through the formation of a Pd-hydroxide active intermediate. This Account evidences the benefits of synergistic collaborations between experimental and computational methods in developing novel transition-metal-catalyzed cross-coupling reactions.

Topics & Concepts

RegioselectivityNucleophileChemistryStereospecificityRing (chemistry)PalladiumAlkylReagentCombinatorial chemistryElectrophileCatalysisOrganic synthesisOrganic chemistryCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsSulfur-Based Synthesis Techniques