Synthesis of Semicyclic Dienes by Modified Julia Olefination of Vinyl Sulfones Derived from Carbohydrates

Abstract

The synthesis of carbohydrate-derived dienes from C-glucosylidene vinyl sulfones by Julia olefination is described.

Key words

modified Julia olefination - vinyl sulfones - dienes - ­carbohydrate - aromatic aldehydes

References and Notes

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9

Typical Procedure and Selected Data for Compound 9: In a 10-mL round-bottomed flask under argon, 7 (100 mg, 0.16 mmol) and 4-chlorobenzaldehyde (22 µL, 1.2 equiv) were dissolved in freshly distilled THF (1 mL) at -78 °C, then a 1 M solution of LiHMDS in THF (383 µL, 2.4 equiv) was added dropwise over 5 min. Stirring was maintained during 30 min at -78 °C and then at r.t. for 1 h. After hydrolysis, the mixture was extracted with EtOAc (3 × 10 mL), dried over Na₂SO₄, concentrated by rotary evaporation and purified by flash chromatography to afford the desired product (63 mg, 0.115 mmol); yield: 72%; yellow liquid; [α]_D ²² -1 (c = 1, acetone); R _f 0.44 (EtOAc-PE, 1:9). ¹H NMR (300 MHz, CD₃COCD₃): δ = 3.89-3.96 (m, 3 H, 2 × H-8, H-6), 4.21-4.26 (m, 1 H, H-7), 4.31 (dd, J = 3.3, 5.7 Hz, 1 H, H-5), 4.61-4.88 (m, 6 H, OCH ₂Ph), 5.25 (d, J = 3.3 Hz, 1 H, H-4), 6.67 (d, J = 15.9 Hz, 1 H, HC=C), 6.94 (d, J = 15.9 Hz, 1 H, HC=C), 7.27-7.40 (m, 17 H, ArH), 7.50 (d, J = 8.7 Hz, 2 H, ArH). ¹³C NMR (75 MHz, CD₃COCD₃): δ = 69.4 (CH₂), 70.9 (CH₂), 73.7 (CH₂), 73.8 (CH₂), 75.3 (CH), 76.9 (CH), 77.9 (CH), 103.4 (CH), 124.9 (CH), 128.2 (C), 128.2 (CH), 128.3 (CH), 128.3 (CH), 128.5 (CH), 128.6 (CH), 128.6 (CH), 129.0 (CH), 129.1 (CH), 129.6 (CH), 133.7 (C), 136.5 (C), 139.6 (C), 139.8 (C), 151.9 (C), 163.2 (C). MS (ESI+): m/z (%) = 575.2 [M + Na]⁺. HRMS (ESI): m/z [M + Na]⁺ calcd for C₃₅H₃₃ClO₄Na: 575.1965; found: 575.1969.