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Stereoselective reduction of the ketone group in α-allyl β-keto esters

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Abstract

Stereoselective reduction of the ketone carbonyl group in α-allyl-substituted β-keto esters with sodium tetrahydridoborate in the presence of 2 equiv of MnCl2 quantitatively afforded the corresponding syn-isomeric alcohols. The reduction of the same substrates with L-selectride [LiBH(s-Bu)3] in anhydrous THF was characterized by low chemoselectivity, and anti-isomeric alcohols were formed in about 50% yield. Under analogous conditions, α-allyl ketones smoothly reacted with L-selectride to give syn-isomeric alcohols in quantitative yield. The corresponding anti isomers were synthesized by the Mitsunobu reaction of the syn isomers with formic acid, followed by alkaline hydrolysis.

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Authors and Affiliations

  1. Timiryazev Moscow Agricultural Academy Russian State Agrarian University, Timiryazevskaya ul. 49, Moscow, 127550, Russia

    V. I. Boev, A. I. Moskalenko, S. L. Belopukhov & N. M. Przheval’skii

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  1. V. I. Boev
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  2. A. I. Moskalenko
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  3. S. L. Belopukhov
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  4. N. M. Przheval’skii
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Correspondence to V. I. Boev.

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Original Russian Text © V.I. Boev, A.I. Moskalenko, S.L. Belopukhov, N.M. Przheval’skii, 2015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51, No. 9, pp. 1279–1286.

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Boev, V.I., Moskalenko, A.I., Belopukhov, S.L. et al. Stereoselective reduction of the ketone group in α-allyl β-keto esters. Russ J Org Chem 51, 1253–1260 (2015). https://doi.org/10.1134/S1070428015090067

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