Cross-Metathesis Approach for Stereocontrolled Synthesis of the C1–C15 Fragment of Rhizopodin

Abstract

The C1–C15 fragment of rhizopodin was synthesized through either Suzuki coupling reaction of vinyl iodide and vinyl boronate or cross-metathesis of a terminal olefin and a diene adduct in the presence of Hoveyda–Grubbs II catalyst.

Key words

cross-metathesis - cross-coupling - stereocontrolled synthesis - conjugated diene - rhizopodin

• References and Notes

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• 21 Procedures for the synthesis of diene 1: Suzuki Cross-Coupling; General Procedure: Vinyl iodide 5 (1.0 equiv), pinacol boronate 4 (1.2 equiv), base (2.0 equiv) and ligand (0.5 equiv) were dissolved in degassed THF (2.0 mL) and palladium catalyst (0.1 equiv) dissolved in degassed THF (1.0 mL) was added by using a cannula. The reaction mixture was stirred at ambient temperature and monitored by TLC. Upon completion of the reaction, it was quenched by addition of sat. aq NH₄Cl (10 mL) and filtered through a pad of Celite, eluted with CH₂Cl₂ (10 mL). The filtrate was concentrated to remove volatiles and the aqueous residue was extracted with CH₂Cl₂ (3 × 30 mL). The combined organic layers were dried over Na₂SO₄ and concentrated under vacuum. The residue was purified by flash column chromatography (EtOAc–hexane, 1:4; R_f = 0.4) to give diene 1 as a colorless oil.Cross-Metathesis; General Procedure: To a solution of alkene 2 (3.0 equiv) and 1,3-diene 3 (1.0 equiv) in degassed solvent (1.5 mL), ruthenium catalyst (0.1 equiv; pre-dissolved in 1.0 mL degassed solvent) was added by using a cannula, and the reaction mixture was stirred at different temperatures and monitored by TLC. When the reaction reached completion, volatiles were removed under vacuum, and compound 1 was obtained after purification by flash column chromatography (EtOAc–hexane, 1:4; R_f = 0.4) as a colorless oil. The analytical data of the product were identical those of the main product of the Suzuki coupling reaction.Analytical Data of 1: [α]_D ²⁵ +8.4 (c 1.1, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 7.54 (s, 1 H), 6.24–5.97 (m, 2 H), 5.77–5.56 (m, 1 H), 5.50–5.31 (m, 1 H), 4.75 (s, 2 H), 4.33–4.14 (m, 2 H), 3.70–3.67 (m, 1 H), 3.66 (s, 3 H), 3.32 (s, 3 H), 3.21 (s, 3 H), 2.72–2.59 (m, 2 H), 2.58–2.45 (m, 2 H), 1.85 (ddd, J = 13.3, 7.9, 5.2 Hz, 1 H), 1.66–1.57 (m, 1 H), 0.91 (s, 9 H), 0.87 (d, J = 8.7 Hz, 9 H), 0.10 (s, 6 H), 0.05 (s, 3 H), 0.03 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 172.19, 162.85, 140.52, 136.03, 132.70, 131.98, 131.81, 129.99, 78.71, 76.08, 66.78, 58.42, 56.86, 55.96, 51.40, 43.40, 42.42, 37.79, 25.76, 18.37, 17.93, –4.49, –4.80, –5.39. HRMS (ESI): m/z [M + Na]⁺ calcd for C₃₀H₅₅NO₇Si₂Na⁺: 620.3410; found: 620.3406.