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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

Contributor(s):
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
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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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Publication History

Article published online:
14 July 2023

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