Stereoselective Synthesis of Coreoside D and Determination of Its Absolute Configuration

Abstract

We report the stereoselective synthesis of (3S)- and (3R)-coreoside D. The conjugated diyne in the C1–C14 moiety was synthesized through two types of palladium-catalyzed cross-coupling reaction. The introduction of the glucopyranose was achieved by a glycosylation reaction using an imidate derivative in the presence of a Lewis acid. The asymmetric center at the C3-position was constructed by the chiral-pool method using d-malic acid. The stereochemistry at the C3-position of the natural product was determined to be R by comparing the [α]_D values of the synthetic stereoisomers with that reported for the natural product.

Key words

asymmetric synthesis - coreoside D - polyacetylene glycoside - palladium catalysis - coupling reaction - glycosylation

• References and Notes

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• 11 (3S)-Coreoside (4a) A 1.02 M solution of NaOMe in MeOH (0.25 mL, 0.255 mmol) was added to a solution of diol (3S)-27 (0.126 mmol) in 1:1 MeOH–THF (4 mL), and the mixture was stirred at r.t. for 1 h, then neutralized with Amberlite IR-120 (hydrogen form). The resulting mixture was filtered through paper and concentrated. The residue was purified by chromatography [silica gel, CH₂Cl₂–MeOH (4:1)] to give a white solid; yield: 35.6 mg [71% from alcohol (S)-8]; mp 40 °C; R_f = 0.25 (CH₂Cl₂–MeOH, 4:1); [α]²¹ _D –31 (c 0.06, MeOH). ¹H NMR (400 MHz, CD₃OD): δ = 1.56–1.83 (m, 4 H), 2.30 (q, J = 7.1 Hz, 2 H), 3.16 (t, J = 8.3 Hz, 1 H), 3.21–3.40 (m, 3 H), 3.62–3.72 (m, 2 H), 3.72–3.81 (m, 1 H), 3.81–3.92 (m, 2 H), 4.14 (dd, J = 4.7, 2.0 Hz, 2 H), 4.34 (d, J = 8.3 Hz, 1 H), 5.66 (d, J = 16.0 Hz, 1 H), 5.83 (d, J = 15.6 Hz, 1 H), 6.35 (dt, J = 15.6, 7.1 Hz, 1 H), 6.37 (dt, J = 16.0, 4.7 Hz, 1 H). ¹³C NMR (100 MHz, CD₃OD): δ = 30.1, 35.4, 38.2, 59.5, 62.68, 62.75, 71.6, 73.1, 74.9, 75.3, 77.8, 77.9, 78.2, 79.7, 81.2, 103.9, 109.0, 109.7, 147.4, 150.0. HRMS (FD): m/z [M]⁺ calcd for C₂₀H₂₈O₈: 396.17842; found: 396.17676. UV (MeOH): λ_max 262, 276, 293, 313 nm.