2-ADAMANTAN-2-YL-PROPAN-2-OL synthesis

22635-58-1
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105419-86-1
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Yield:105419-86-1 78%

Reaction Conditions:

with methyllithium in diethyl ether at 0 - 20;Inert atmosphere;

Steps:

2-(2-Adamantyl-2-propanol, 32.

To a stirred solution of sodium ethoxide (220 mg, 9.60mmol) in absolute ethanol (5 mL) and anhydrous THF (11 mL), a solution of 2-adamantanone (960 mg, 6.40 mmol) and toluenesulfonyl methylisocyanide (TOSMIC) (1.49 g,7.68 mmol) in anhydrous THF (25 mL) at room temperature. The mixture was stirred at room temperature for 2 h, then solvent was evaporated in vacuo andwater (15 mL) was added. The mixture was extracted with ether and the organic solution was dried (Na₂SO₄). Solvent was removed to afford quantitatively 2-cyanoadamantane 4 (ethanol - water). To a stirred solution of 2-cyanoadamantane 4 (350 mg, 2.17 mmol) in anhydrous ether was added during a 2 min period, under an argon atmosphere, a solution of MeLi 1.6 M in ether (4.1 mL, 6.56 mmol) at 0 °C. The yellow complex formed was stirred for 90 min at ambienttemperature and hydrolyzed with water (8 mL) at 0 C. The residue was treated with a mixture of acetone (5 mL) and HCl 6N (5 mL) and the mixture was refluxed for 2 h. Acetone was removed in vacuo and the resulting mixture was extracted with ether. The organic solution was washed with water and brine, was dried (Na₂SO₄) and evaporated in vacuo to afford 2-acetyladamantane 34 (302 mg, 78 %). To a stirred solution of 2-acetyladamantane 34 (590 mg, 3.31 mmol) in anhydrous ether (40 mL) was added dropwise, under an argon atmosphere, a solution of MeLi 5 % in ether (4.4 mL, 10.0 mmol) at 0 °C. The mixture was stirred overnight at ambient temperature, then a saturated solution of NH₄Cl (50 mL) was added at 0 °C. The organic phase was separated, washed with water, brine and dried over Na₂SO₄. After solvent evaporation the liquid alcohol 32 (502 mg, 78 %).

References:

Kolocouris, Antonios;Koch, Andreas;Kleinpeter, Erich;Stylianakis, Ioannis [Tetrahedron,2015,vol. 71,# 16,p. 2463 - 2481] Location in patent:supporting information