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DOI: 10.1055/s-0041-1737727
Iridium-Catalyzed Photosensitization of β-Dicarbonyls to Access Medium-Sized Rings
Dynamic Kinetic Sensitization of β-Dicarbonyl Compounds – Access to Medium-Sized Rings via a De Mayo-Type Ring Expansion.
Angew. Chem. Int. Ed. 2021;
DOI: 10.1002/anie.202112695

Significance
The authors report the synthesis of medium-sized rings via a De Mayo-type ring expansion. The use of fac-[Ir(CF3-pmb)3], a tris-cyclometalated complex bearing three N-heterocyclic carbene ligands, as the photosensitizer is crucial for the reaction’s success.
Comment
The reaction tolerates mono, 1,1-, and 1,2-disubstituted olefins as coupling partners. Heavily substituted olefins could not undergo the necessary retro-aldol reaction. Density functional theory suggests that the more nucleophilic α-hydroxy radical adds preferentially to the alkene to begin the stepwise cycloaddition.
Publikationsverlauf
Artikel online veröffentlicht:
18. Januar 2022
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