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Synfacts 2022; 18(02): 0153
DOI: 10.1055/s-0041-1737727
Metals in Synthesis

Iridium-Catalyzed Photosensitization of β-Dicarbonyls to Access Medium-Sized Rings

Contributor(s):
Mark Lautens
,
Bijan Mirabi
Paulisch TO, Mai LA, Strieth-Kalthoff F, James MJ, Henkel C, Guldi DM, *, Glorius F. * Westfälische Wilhelms-Universität Münster, Germany
Dynamic Kinetic Sensitization of β-Dicarbonyl Compounds – Access to Medium-Sized Rings via a De Mayo-Type Ring Expansion.

Angew. Chem. Int. Ed. 2021;
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Key words

iridium catalysis - photosensitization - De Mayo reaction - medium-sized rings

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.


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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.


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Publication History

Article published online:
18 January 2022

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