LiAlH4 (18.7 g, 492 mmol) was added to a 2 L three-necked round-bottomed flask equipped with a top stirrer, thermocouple, dropping funnel, and nitrogen inlet and cooled to 0 °C, followed by the addition of anhydrous THF. 4-Hydroxytetrahydro-2H-pyran-4-carbonitrile (25.0 g, 196 mmol) was slowly added dropwise to the reaction mixture over a period of 1 h. The reaction was carried out in a 250 mL) solution. After the dropwise addition, the reaction mixture was warmed to room temperature and the dropping funnel was replaced with a reflux condenser and heated to reflux at 70 °C for 4 hours. Upon completion of the reaction, the mixture was cooled to room temperature and further cooled to -10 °C in a dry ice acetone bath, followed by quenching the reaction with 2N NaOH solution (150 mL) until a white precipitate appeared. The reaction mixture was warmed to room temperature, diluted with ethyl acetate (500 mL) and stirred for 10 minutes. The precipitated solid was filtered through a diatomaceous earth pad and the diatomaceous earth pad was washed with ethyl acetate (300 mL). The filtrate was concentrated under reduced pressure to give a gelatinous liquid, which was dissolved in methyl tert-butyl ether (MTBE, 100 mL) and cooled to 0°C. A dioxane solution (100 mL) in 4N HCl was added dropwise to this solution and stirred at 0 °C for 30 min, followed by continued stirring at room temperature for 30 min. The precipitated solid was collected by vacuum filtration and dried over a constant flow of N2 gas to afford the target product 4-(aminomethyl)tetrahydro-2H-pyran-4-ol hydrochloride (21.0 g, 64% yield) as an off-white solid; Mass Spectrum (MS): m/z = 132 (M+H+).
