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Synfacts 2023; 19(08): 0799
DOI: 10.1055/s-0042-1752838
Metals in Synthesis

The Saegusa–Ito Oxidation of Silyl Enol Ethers to α,β-Unsaturated Carbonyl Compounds

Rezensent(en):
Martin Oestreich
,
Hendrik F. T. Klare
,
Emilio Acuña Bolomey
Ito Y, Hirao T, Saegusa T. * Kyoto University, Japan
Synthesis of α,β-Unsaturated Carbonyl Compounds by Palladium(II)-Catalyzed Dehydrosilylation of Silyl Enol Ethers.

J. Org. Chem. 1978;
43: 1011-1013
DOI: 10.1021/jo00399a052.
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Key words

palladium catalysis - silyl enol ethers - α,β-unsaturated carbonyls

Significance

The Saegusa–Ito oxidation, introduced in 1978, is a synthetically important transformation, allowing to convert silyl enol ethers into the corresponding α,β-unsaturated carbonyl compounds. With acyclic and large ring substrates, the reaction is completely stereoselective towards the E-isomer, regardless of the stereochemistry of the starting silyl enol ether.


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Comment

The original reaction was barely substoichiometric, using 0.5 equiv of Pd(OAc)2 and p-benzoquinone as the oxidant. Reducing the catalyst loading would systematically result in lower yields. One way to circumvent this drawback is the Larock modification (Tetrahedron Lett. 1995, 36, 2423). In this protocol, the reaction is carried out in DMSO under an oxygen atmosphere, which reoxidizes Pd(0) back to Pd(OAc)2.


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Publikationsverlauf

Artikel online veröffentlicht:
14. Juli 2023

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