Reacción #944246

Ecuación de reacción

trimethylsilyl cyanide

3-oxo-indan-1-carboxylic acid methyl ester

acetonitrile

→

3-cyano-3-trimethylsilanyloxy-indan-1-carboxylic acid methyl ester

Rendimiento 97.0%

Disolventes

toluene

sodium bicarbonate

toluene

Condiciones de reacción

Tratamiento posterior

1. 1
   TemperaturaThe reaction mixture was then cooled to room temperature
2. 2
   Otrowere separated
3. 3
   LavadoThe organic layer was washed with another 8 mL of a saturated aqueous sodium bicarbonate solution
4. 4
   SecadoThe organic layer was dried over anhydrous sodium sulfate
5. 5
   Concentraciónconcentrated in vacuo

Procedimiento

To a solution of 3.80 g of 3-oxo-indan-1-carboxylic acid methyl ester (20.0 mmol, 1 equivalent) in 6 mL of toluene and 2 mL of acetonitrile was added 192 mg of zinc iodide (0.600 mmol, 0.03 equivalent) followed by 3.47 mL of trimethylsilyl cyanide (26.0 mmol, 1.3 equivalent). The reaction mixture was heated to 50° C. for 5 hours. The reaction mixture was then cooled to room temperature and diluted with 12 mL of toluene and 8 mL of a saturated aqueous sodium bicarbonate solution. After stirring the mixture for 1 hour the layers were separated. The organic layer was washed with another 8 mL of a saturated aqueous sodium bicarbonate solution followed by 8 mL of a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo to give 3-cyano-3-trimethylsilanyloxy-indan-1-carboxylic acid methyl ester as an oil (5.61 g, 97%). The silylated cyanohydrin title compound was obtained as a mixture of two diastereomers in a 2:1 ratio: 1H NMR (400 MHz, CDCl3): (major isomer) δ 7.54–7.50 (m, 1H), 7.42–7.38 (m, 3H), 4.14 (t, J=7.7 Hz, 1H), 3.78 (s, 3H), 3.01 (dd, J=13.3, 7.5 Hz, 1H), 2.79 (dd, J=13.3, 7.5 Hz, 1H), 0.26 (s, 9H); (minor isomer) 67.59–7.55 (m, 1H), 7.48–7.44 (m, 3H), 4.29 (t, J=7.5 Hz, 1H), 3.78 (s, 3H), 3.03 (dd, J=13.7, 7.5 Hz, 1H), 2.70 (dd, J=13.7, 7.5 Hz, 1H), 0.14 (s, 9H); 13C NMR (100 MHz, CDCl3): (unassigned) δ 172.3, 172.0, 142.3, 142.1, 140.1, 138.8, 130.8, 130.5, 129.1, 128.9, 125.8, 125.6, 124.7, 124.3, 120.8, 120.6, 75.4, 75.3, 52.7, 52.7, 47.4, 46.8, 45.6, 45.3, 1.4, 1.3; IR (neat, cm−1): 2956, 1739, 1477, 1436, 1253, 1197, 1169, 1135, 1092, 1033, 1011, 880, 843, 756, 623; Anal. Calcd for C15H19NO3Si: C, 62.25; H, 6.62; N, 4.84; Found: C, 62.20; H, 6.53; N, 4.92.

Fuente