A Straightforward Synthesis of (3S)-4-Methoxybutane-1,3-diol and its Use as Chiral Auxiliary for the Preparation of (pS)-1-(Diphenylphosphino)-2-formyl-1′,2′,3′,4′,5′-pentamethylferrocene

Abstract

(3S)-4-Methoxybutane-1,3-diol [(S)-4], an important auxiliary for the synthesis of planar-chiral metallocenes, has been obtained from (S)-1,2,4-butanetriol via formation of an isomerically pure acetal of p-nitrobenzaldehyde, O-methylation and hydrolysis. Diol (S)-4 was used in a synthesis of the new planar-chiral ferrocene (pS)-1-(diphenylphosphino)-2-formyl-1′,2′,3′,4′,5′-pentamethylferrocene [(pS)-9].

Key words

acetals - asymmetric synthesis - chiral pool - lithiation - metallocenes

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9

Crystal Data for (pS)-9: C₂₈H₂₉FeOP, MW = 468.33, monoclinic, space group P2₁/c, a = 9 3345 (1) Å, b = 14 1901 (2) Å, c = 27 7268 (3) Å, β = 98 691 (1)°, V = 3630.45 (8) ų, Z = 6, D_calcd = 1.285 g/cm³, crystal size 0.28 × 0.26 × 0.26 mm³. Intensity data were collected at 200(2) K with Mo-K_α radiation (λ = 0.71073 Å). A total of 16501 independent reflections were measured in range 0.74 < Θ < 26.00° and 14474 reflections were considered as observed applying the condition I > 2σ(I). The crystal used for X-ray diffraction was grown in a solution of CH₂Cl₂ and pentane. All calculations were performed using the SHELXL-97 program. Structure solved by direct methods and refined against F² with a Full-matrix least-squares algorithm. Hydrogen atoms were treated using appropriate riding models. Flack absolute structure parameter 0.002 (9), goodness of fit 1.02 for observed reflections, final residual values R1 (F) = 0.040, wR2 (F²) = 0.096 for observed reflections, residual electron density -0.47 to 1.13 e Å^-3. CCDC 296455 contains the supplementary crystallographic data for this structure. The data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK; fax: [phone]; email: [e-mail]).