Compound 13

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InChIKey AUOVZVQMDOUGEC-WIKAKEFZSA-N

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

The intermediate (2S,3S)-2-(iodomethyl)-5-methoxytetrahydrofuran-3-ol was prepared from the compound 12 according to a literature procedure (Skaanderup, P. R., Poulsen, C. S., Hyldtoft, L., Jørgensen, M. R. & Madsen, R. Regioselective conversion of primary alcohols into iodides in unprotected methyl furanosides and pyranosides. Synthesis 1721−1727 (2002)).

(2S,3S)-2-(iodomethyl)-5-methoxytetrahydrofuran-3-ol (50.0 g, 194 mmol) and triethylsilyl chloride (34.5 mL, 203 mmol) were disolved in CH2Cl2 (50 mL) and the mixture cooled with stirring to 0 °C. Pyridine (31.3 mL, 388 mmol) was added dropwise and the solution allowed to stir for ca. 1.5 hours. The reaction was diluted with 50% diethyl ether in petroleum ether and quenched with water. The combined organic phases were dried (MgSO₄), filtered and concentrated in vacuo to afford the crude product. Purification by flash chromatography (silica gel, 0–5 % diethyl ether in petroleum ether) afforded an anomeric mixture (α/β ratio 3:2) of the triethylsilyl ether 13 (71.0 g, 98%) as a colorless oil: R_f = 0.35 (TLC, 1:9 diethyl ether/petroleum ether); ¹H-NMR (500 MHz, CDCl₃) δ 5.10 (dd, J = 5.4, 1.9 Hz, 1H (minor)), 4.99 (dd, J = 5.9, 2.8 Hz, 1H (major)), 4.34 (app. dt, J = 6.3, 4.1 Hz, 1H (minor)), 3.97–3.93 (m, 1H (major) + 1H (minor)), 3.59–3.56 (m, 1H (major)), 3.47 (dd, A of ABX, J_AB = 10.9 Hz, J_AX = 3.6 Hz, 1H (major)), 3.38 (s, 3H (major)), 3.36 (s, 3H (minor)), 3.29 (dd, B of ABX, J_AB = 10.9 Hz, J_BX = 4.6 Hz, 1H (major)), 3.27 (dd, A of ABX, J_AB =10.2 Hz, J_AX = 6.7 Hz, 1H (minor)), 3.23 (dd, B of ABX, J_AB =10.4 Hz, J_BX = 6.3 Hz, 1H (minor)), 2.47 (ddd, A of ABXY, J_AB = 13.9 Hz, J_AX = 8.4 Hz, J_AY = 5.7 Hz, 1H (major)), 2.20 (ddd, A of ABXY, J_AB = 13.3 Hz, J_AX = 6.6 Hz, J_AY = 1.9 Hz, 1H (minor)), 2.07 (app. dt, B of ABX2, J_AB = 13.3 Hz, J_BX = 5.8 Hz, 1H (minor)), 1.84 (ddd, B of ABXY, J_AB = 13.6 Hz, J_BX = 5.7 Hz, JBY = 2.8 Hz, 1H (major)), 0.94 (t, J = 8.0 Hz, 9H (major) + 9H (minor)), 0.60 (app. quintet, J = 8.0 Hz, 6H (major) + 6H (minor)); ¹³C-NMR (125 MHz, CDCl₃) δ 105.32 (o), 104.27 (o), 86.00 (o), 80.85 (o), 75.43 (o), 74.97 (o), 55.42 (o), 42.62 (e), 42.24 (e), 8.19 (e), 8.06 (e), 6.87 (o), 6.85 (o), 4.79 (e); IR (neat) 2954 (m), 2910 (w), 2877 (w), 2830 (w), 1458 (w), 1413 (w), 1377 (w), 1240 (w), 1201 (w), 1184 (w), 1098 (s), 1066 (m), 1030 (s), 1017 (s), 959 (s), 837 (m), 725 (s), 686 (m) cm⁻¹; HRMS (ESI, [M+Na]⁺) calcd for C₁₂H₂₅O₃Si¹²⁷INa 395.0515, found 395.0503.