Samarium(II) di-iodide, which is a strong one-electron transfer reducing agent, is effective for the reductive coupling of α,β-unsaturated esters with carbonyl compounds, whereby substituted γ-lactones can easily be prepared in good to excellent yields under very mild conditions. Two mole equiv. of samarium(II) di-iodide to each mole equiv. of starting substrate always give reasonable yields. The presence of an alcohol is essential in the reaction, complex unidentified products being formed in the absence of an alcohol; t-butyl alcohol gave more satisfactory results than methanol and ethanol. The alcohol acts as a proton donor, the use of MeOD leading to a deuteriated γ-lactone. The reaction is applicable to both aliphatic and aromatic ketones or aldehydes, whereas the electrochemical method is limited to aliphatic substrates. The diastereoselectivity is examined in the reaction of 4-t-butylcyclohexanone with ethyl acrylate; an anti-isomer is produced predominantly (syn :anti= 1 : 9) as the result of selective axial attack. The reaction may proceed by a radical mechanism, and reaction may not involve a samarium ester homoenolate. The reaction is extended to the intramolecular reaction of an α,β-unsaturated keto ester (8-oxonon-2-enoate) leading to the ready synthesis of a bicyclic γ-lactone.
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Journal of the Chemical Society, Perkin Transactions 1
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