Experimental and Computational Studies on Cobalt(I)‐Catalyzed Regioselective Allylic Alkylation Reactions

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] ar...

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Published in:Angewandte Chemie 2023-11, Vol.135 (46), p.n/a
Main Authors: Andreetta, Philip, Martin, Robert T., Souilah, Charafa, Rentería‐Gómez, Ángel, Song, Zhihui, Khorramshahi Bayat, Yas, Ivlev, Sergei, Gutierrez, Osvaldo, Casitas, Alicia
Format: Article
Language:English
Subjects:
Alkylation
Allylic Alkylation Reaction
Carbonates
Carbonyl compounds
Catalysts
Chemical reactions
Chemical synthesis
Chemistry
Cobalt
Cobalt Catalysis
Cobalt compounds
Computer applications
Coordination Cobalt(I) Complexes
Phosphine
Phosphines
Reaction Mechanism
Regioselectivity
Theoretical Calculations
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Summary: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. A cobalt(I)‐catalyzed regioselective allylic alkylation of tertiary allylic carbonates with 1,3‐dicarbonyl compounds is described. The alkylated products are obtained in high yields and with excellent selectivity towards the kinetic branched regioisomer. Mechanistic insights by combining experimental and computational investigations support a Co(I)/Co(III) catalytic cycle.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202310129