Mechanistic insight into cobalt-mediated [2 + 2 + 2]-cycloaddition reactions with γ-alkylidenebutenolide and γ-alkylidenebuterolactam as 2π partners.

Dalton transactions (Cambridge, England : 2003)(2023)

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摘要
The molecular complexity of recently reported cobalt(III) polycyclic complexes, resulting from an intramolecular formal (2 + 2 + 3) cycloaddition reaction on an enediyne containing a lactone moiety, has prompted us to computationally review the mechanisms of cobalt cycloaddition reactions with γ-alkylidenebutenolide or γ-alkylidenebuterolactam as 2π partners. Computed mechanisms are compared, leading to either cobalt(III)- or cobalt(I)-spiro complexes depending of both the nature of the reaction (intra- vs. intermolecular pathway) and the nature of the 2π partner (γ-alkylidenebutenolide vs. γ-alkylidenebuterolactam). These proposed mechanisms are supported by experiments, allowing us to report the synthesis and characterization of the predicted compounds.
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关键词
reactions,2π partners,cobalt-mediated,]-cycloaddition
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