Synthesis of Methylene Exoglycals Using a Modified Julia Olefination

Abstract

A new route to exomethylene sugars is reported. The use of a two-step coupling-elimination procedure allows successful Julia olefination of sugar-derived lactones.

Key words

glycals - olefination - carbohydrate - alkenes - lactones

References

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16

All compounds were characterised by NMR spectroscopy and HRMS. Data were identical to those reported in the literature.
Data for compound 5: ¹H NMR (300 MHz, CDCl₃): δ = 4.39 (d, 1 H, J = 4.3 Hz, H-2), 4.23 (s, 1 H, H-1′a), 4.05 (m, 2 H, H-3 and H-4), 3.95 (s, 1 H, H-1′b), 3.71 (dd, 1 H, J = 3.2 Hz, J = 11.5 Hz, H-5a), 3.63 (dd, 1 H, J = 3.4 Hz, H-5b), 0.90 (m, 27 H, CH₃), 0.59 (m, 18 H, CH₂). ¹³C NMR (75 MHz, CDCl₃): δ = 4.7, 5.2, 5.5, 7.1, 7.2, 7.3, 62.4, 72.7, 73.0, 82.6, 85.9, 163.4. IR: 1678 cm^-1 (C=C). [α]_D +15 (c 1, CHCl₃). HRMS (CI-MS): m/z calcd for C₂₄H₅₂O₄Si₃ [M + H]⁺: 489.3252; found: 489.3257