Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume -, Issue -, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202310129
Keywords
Allylic Alkylation Reaction; Cobalt Catalysis; Coordination Cobalt(I) Complexes; Reaction Mechanism; Theoretical Calculations
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In this study, a cobalt(I)-catalyzed regioselective allylic alkylation reaction of tertiary allyl carbonates with 1,3-dicarbonyl compounds was developed. A series of tetrahedral cobalt(I) complexes with commercially available bidentate bis(phosphine) ligands were synthesized and investigated as catalysts. The results showed that one specific catalyst exhibited high yields and excellent regioselectivity for the branched product in the alkylation of various tertiary allyl carbonates.
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.
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