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Silylation of γ-nitro ketones as a convenient approach to the synthesis of 2-[N,N-bis(silyloxy)amino]-2,3-dihydrofurans and conjugated enoximes

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Abstract

Silylation of γ-nitro ketones of the general formula R1COCH(R2)CH(R3)CH(R4)NO2 proceeded stereoselectively to give 2-[N,N-bis(trimethylsilyloxy)amino]-2,3-dihydrofurans, conjugated enoximes, silylation products of the carbonyl group or both functional groups, or N,N-bis(trimethylsilyloxy)enamine depending on the nature and positions of the substituents in the carbon skeleton. Dihydrofuran derivatives are formed for R1 = Ar or cyclo-C3H5. Enoximes are generated as the silylation products of the starting ketones with enhanced β-proton mobility (R3 = CO2Me or 4-NO2C6H4). The presence of an alkyl group at the carbonyl function (R1 = Alk) is favorable for the formation of enoximes. Finally, the introduction of a substituent at the α position with respect to the nitro group (R4 = Me, CO2Me, or Ph) leads to the formation of silyl enolates. Under the action of NH4F in MeOH, dihydrofurans can be transformed into substituted furans in moderate yields.

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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation

    K. P. Birin, A. A. Tishkov, S. L. Ioffe, Yu. A. Strelenko & V. A. Tartakovsky

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  1. K. P. Birin
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  2. A. A. Tishkov
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  3. S. L. Ioffe
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  4. Yu. A. Strelenko
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  5. V. A. Tartakovsky
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Birin, K.P., Tishkov, A.A., Ioffe, S.L. et al. Silylation of γ-nitro ketones as a convenient approach to the synthesis of 2-[N,N-bis(silyloxy)amino]-2,3-dihydrofurans and conjugated enoximes. Russian Chemical Bulletin 52, 647–658 (2003). https://doi.org/10.1023/A:1023958806825

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