Reaktion #731296

Reaktionsgleichung

pinacol boronate

3-ethyl-3-(6-thiophen-2-yl-hexyloxymethyl)oxetane

n-butyllithium

→

product

Ausbeute 72.3%

2-{5-[6-(3-Ethyl-oxetan-3-ylmethoxy)-hexyl]-thiophen-2-yl}-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane

Ausbeute 72.3%

Lösungsmittel

THF

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONAfter complete addition
2. 2
   SonstigeThe reaction was quenched with water
3. 3
   Extraktionthe reaction mixture was extracted with ethyl acetate (3×70 ml)
4. 4
   WaschenThe combined organic extracts were washed with water, brine
5. 5
   Trocknendried over sodium sulphate
6. 6
   SonstigeThe solvent was removed under reduced pressure
7. 7
   Sonstigethe residue was purified by column chromatography on silica
8. 8
   Wascheneluting with petroleum ether/ethyl acetate (9:1)

Vorschrift

To a stirred solution of 3-ethyl-3-(6-thiophen-2-yl-hexyloxymethyl)oxetane (6.0 g, 21.28 mmol) in dry THF (70 ml) was added n-butyllithium (2.5 M in hexanes, 8.10 ml, 21.28 mmol) dropwise at −78° C. under nitrogen. After complete addition, the mixture was allowed to warm to room temperature, with stirring, over 2 h, followed by the addition of pinacol boronate (3.96 g, 21.28 mmol). The resultant mixture was stirred overnight at room temperature. The reaction was quenched with water, and the reaction mixture was extracted with ethyl acetate (3×70 ml). The combined organic extracts were washed with water, brine, and dried over sodium sulphate. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica, eluting with petroleum ether/ethyl acetate (9:1), to afford the product as a yellow oil (6.28 g, 72%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.45 (d, J=3.4 Hz, 1H, Ar—H), 6.85 (d, J=3.4 Hz, 1H, Ar—H), 4.44 (d, J=5.8 Hz, 2H, OCH2), 4.36 (d, J=5.8 Hz, 2H, OCH2), 3.51 (s, 2H, OCH2), 3.45 (t, J=6.4 Hz, 2H, OCH2), 2.83 (t, J=7.6 Hz 2H, ArCH2), 1.32-1.77 (m, 22H, CH2 and CH3), 0.88 (t, J=7.4 Hz, 3H, CH3); δ (ppm) 153.5 (quat.), 145.6 (quat.), 137.3 (CH), 125.9 (CH), 83.9 (quat.), 78.6 (OCH2), 73.4 (OCH2), 71.5 (OCH2), 43.4 (quat.), 31.6 (CH2), 30.1 (CH2), 29.4 (CH2), 28.8 (CH2), 26.8 (CH2), 25.9 (CH2), 24.8 (CH3), 8.2 (CH3); MS (m/e): 408 (M+, 0.5%), 223 (27), 165 (30), 141 (35), 123 (100), 97 (52).

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