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Experimental and Computational Studies on Cobalt(I)-Catalyzed Regioselective Allylic Alkylation Reactions
Authors:Philip Andreetta  Dr. Robert T. Martin  Charafa Souilah  Dr. Ángel Rentería-Gómez  Dr. Zhihui Song  Yas Khorramshahi Bayat  Dr. Sergei Ivlev  Prof. Dr. Osvaldo Gutierrez  Prof. Dr. Alicia Casitas
Affiliation:1. Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany;2. Department of Chemistry and Biochemistry, University of Maryland, College Park. 8051 Regents Dr, College Park, Maryland, 20742 USA;3. Department of Chemistry, Texas A&M University, College Station, Texas, 77843 USA
Abstract:Here, we report the development of cobalt(I)-catalyzed regioselective allylic alkylation reactions of tertiary allyl carbonates with 1,3-dicarbonyl compounds. A family of well-defined tetrahedral cobalt(I) complexes bearing commercially available bidentate bis(phosphine) ligands [(P,P)Co(PPh3)Cl] are synthesized and explored as catalysts in allylic alkylation reactions. The catalyst [(dppp)Co(PPh3)Cl] (dppp=1,3-Bis(diphenylphosphino)propane) enables the alkylation of a large variety of tertiary allyl carbonates with high yields and excellent regioselectivity for the branched product. Remarkably, this methodology is selective for the activation of tertiary allyl carbonates even in the presence of secondary allyl carbonates. This contrasts with the selectivity observed in cobalt-catalyzed allylic alkylations enabled by visible light photocatalysis. Mechanistic insights by means of experimental and computational investigations support a Co(I)/Co(III) catalytic cycle.
Keywords:Allylic Alkylation Reaction  Cobalt Catalysis  Coordination Cobalt(I) Complexes  Reaction Mechanism  Theoretical Calculations
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