Effect of carbonates/phosphates as nucleophilic catalysts in dimethylformamide for efficient cyanosilylation of aldehydes and ketones

Prakash et al. 10.1073/pnas.0611309104.

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General procedure for the addition of TMSCN to carbonyl compounds under nucleophilic catalysis.

To a solution of carbonyl compound (1 mmol) and the nucleophilic catalyst (1-5 mol%) in dry DMF (3 ml), TMSCN (1.2-1.5 equivalent) was added and stirred vigorously at room temperature. After the completion of the reaction (monitored by TLC) the mixture was poured in brine solution (15 ml) and extracted with CH2Cl2 (3 ´ 30 ml). Organic extract was washed with brine solution and dried over anhydrous Na2SO4. Removal of the solvent and purification by column chromatography (using hexane-ethyl acetate (4:1)) afforded the pure TMS protected alcohols.

Compound 2a: Yield 85%; Colorless liquid. dH (400 MHz, CDCl3) 0.22 (s, 9H), 5.49 (s, 1H), 7.37-7.45 (m, 5H). dC (100.5 MHz, CDCl3) -0.39, 63.52, 119.09, 126.23, 128.81, 129.22, 136.17. MS (EI), m/z 204.8 (M+), 189.8 (M+ -CH3).

Compound 2b: Yield 95%; Light yellow solid, mp (169-172°C). dH (400 MHz, CDCl3) 0.09 (s, 9H), 6.93 (s, 1H), 7.46 (dd, J = 6.64 Hz, J = 8.39 Hz, 2H), 7.59 (ddd, J = 6.54 Hz, J = 8.88 Hz, J = 1.37 Hz, 2H), 7.96-8.12 (m, 2H), 8.46-8.52 (m, 3H). dC (100.5 MHz, CDCl3) -0.28, 57.98, 119.74, 123.43, 125.13, 125.82, 127.14, 129.23, 129.39, 130.49, 131.34. MS (EI), m/z 305.9 (M+), 289.9 (M+ -CH3).

Compound 2c: Yield 90%; Off-white solid, mp (105-107°C). dH (400 MHz, CDCl3) 0.24 (s, 9H), 5.63 (s, 1H),7.48-7.56 (m, 3H), 7.81-7.93 (m, 4H). dC (100.5 MHz, CDCl3) -0.28, 63.79, 119.12, 123.56,125.64, 126.65, 126.84, 127.70,128.14, 129.0, 132.87, 133.47. MS (EI), m/z 254.9 (M+), 239.9 (M+ -CH3).

Compound 2d: Yield 96%; Colorless liquid. dH (400 MHz, CDCl3) 0.21 (s, 9H), 5.43 (s, 1H), 7.32 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8.4 Hz, 2H). dC (100.5 MHz, CDCl3) -0.35, 62.93, 118.67, 123.40, 127.88, 132.04, 135.27. MS (EI), m/z 285.7 (M+), 267.6 (M+ -CH3).

Compound 2e: Yield 80%, Colorless liquid. dH (400 MHz, CDCl3) 0.14 (s, 9H), 3.(s, 1H), 7.20 (dd, J = 8.98 Hz, J = 7.03 Hz, 1H), 7.29 (d, J = 8.98 Hz, 1H), 7.30(d, J = 7.03 Hz, 1H). dC (100.5 MHz, CDCl3) -0.43, 59.35, 117.41, 129.26, 131.13, 131.18, 135.34. MS (EI), m/z 272.8 (M+), 257.8 (M+ -CH3).

Compound 2f: Yield 91%, Colorless liquid. dH (400 MHz, CDCl3) d 0.14 (s, 9H), 2.34 (s, 3H), 5.45 (s, 1H), 7.18 (d, J = 8.39 Hz, 2H), 7.34 (d, J = 8.20 Hz, 2H). dC (100.5 MHz, CDCl3) -0.41, 21.01, 63.38, 119.18, 126.23, 129.42, 133.28, 139.14. MS (EI), m/z 218.6 (M+), 203.6 (M+ -CH3).

Compound 2g: Yield 84%, Colorless liquid. dH (400 MHz, CDCl3) 0.21 (s, 9H), 3.80 (s, 3H), 5.44 (s, 1H), 6.92 (d, J = 8.6 Hz, 2H), 7.38(d, J = 8.6 Hz, 2H). dC (100.5 MHz, CDCl3) -0.33, 55.22, 63.24, 114.16, 119.28, 127.85, 128.36, 160.24. MS (EI), m/z 234.8 (M+), 219.8 (M+ -CH3).

Compound 4a: Yield 96%, Colorless liquid. dH (400 MHz, CDCl3) 0.14 (s, 9H), 7.28-7.35 (m, 6H), 7.48-7.51 (m, 4H). dC (100.5 MHz, CDCl3) 0.86, 76.28, 120.65, 125.82, 128.49, 128.60, 141.85. MS (EI), m/z 281.9 (M+), 265.8 (M+ -CH3).

Compound 4b: Yield 87% Colorless liquid, dH (400 MHz, CDCl3) 0.15 (s, 9H), 7.32-7.39 (m, 3H), 7.47-7.50 (m, 2H), 7.72 (d, J = 9.0Hz, 2H), 8.21 (d, J = 9.0 Hz, 2H). dC (100.5 MHz, CDCl3) 0.75, 75.68, 119.59, 123.75, 125.67, 126.59, 128.88, 129.26, 140.34, 147.70, 148.73. MS (EI), m/z 325.7 (M+), 310.4 (M+ -CH3).

Compound 4c: Yield 94%, Colourless liquid. dH (400 MHz, CDCl3) 0.14 (s, 9H), 7.33-7.38 (m, 5H), 7.46-7.49 (m, 4H). dC (100.5 MHz, CDCl3) 0.88, 75.83, 120.19, 122.81, 125.77, 127.51, 128.66, 128.88, 131.67, 141.19, 141.27. MS (EI), m/z 361.8 (M+), 345.8 (M+ -CH3).

Compound 4d: Yield 95%, Colourless liquid. dH (400 MHz, CDCl3) 0.14 (s, 9H), 7.30-7.35 (m, 5H), 7.42-7.49 (m, 4H). dC (100.5 MHz, CDCl3) 0.85, 75.76, 120.25, 125.76, 127.20, 128.64, 128.69, 128.86, 134.59, 140.64, 141.33. MS (EI), m/z 314.9 (M+), 299.8 (M+ -CH3).

Compound 4e: Yield 96%, Colourless liquid. dH (400 MHz, CDCl3) 0.17 (s, 9H), 3.77 (s, 3H), 6.88 (d, J = 9.0 Hz, 2H), 7.28-7.38 (m, 3H), 7.43 (d, J = 9.0 Hz, 2H), 7.50-7.56 (m, 2H). dC (100.5 MHz, CDCl3) 0.83, 55.11, 75.88, 113.69, 120.76, 125.74, 127.28, 128.39, 128.46, 133.90, 142.06, 159.66. MS (EI), m/z 311.9 (M+), 295.7 (M+ -CH3).

Compound 4f: Yield 93%, Colourless liquid. dH (400 MHz, CDCl3) 0.16 (s, 9H), 2.34 (s, 3H), 6.87-6.90 (m, 2H), 7.30-7.60 (m, 5H), 7.50-7.53 (m,2H). dC (100.5 MHz, CDCl3) 0.89, 21.03, 76.16, 120.78, 125.78, 125.81, 128.45, 128.51, 129.15, 138.51, 138.99, 142.06. MS (EI), m/z 295.0 (M+), 279.8 (M+ -CH3).

Compound 4g: Yield 94%, Colorless liquid. dH (400 MHz, CDCl3) 0.17 (s, 9H), 1.84 (s, 3H) 7.33-7.40 (m, 3H), 7.53-7.56 (m, 2H).dC (100.5 MHz, CDCl3) 0.96, 33.48, 71.52, 121.53, 124.52, 128.55, 128.58, 141.90. MS (EI), m/z 219.0 (M+), 203.9 (M+ -CH3).

Compound 4h: Yield 98% Colorless liquid, dH (400 MHz, CDCl3) 0.20 (s, 9H), 1.83(s, 3H), 7.66-7.71 (m, 4H);); dC (100.5 MHz, CDCl3) 0.87, 33.43, 71.10, 120.95, 123.8 (q, 1J(C-F) = 271.4 Hz), 125.06, 125.68 (q, 3J(C,F) = 3.83 Hz), 130.96 (q, 2J(C,F) = 32.72Hz), 146.11. 19F NMR d -63.17. MS (EI), m/z 286.7 (M+), 271.7 (M+ -CH3).

Compound 4i: Yield 81%, Light yellow liquid. dH (400 MHz, CDCl3) 0.23 (s, 9H), 1.03 (t, J = 7.4 Hz, 6H), 1.76 (q, J = 7.4 Hz, 2H), 1.77 (q, J = 7.6 Hz, 2H). dC (100.5 MHz, CDCl3) 1.24, 8.32, 33.47, 74.28, 121.38. MS (EI), m/z 184.3 (M+), 169.6 (M+-CH3).

Compound 4j: Yield 80%; Light yellow liquid, dH (400 MHz, CDCl3) 0.24 (s, 9H), 1.50-2.20 (m, 10H)); dC (100.5 MHz, CDCl3) 1.34, 22.59, 24.46, 39.29, 70.58, 121.91. MS (EI), m/z 196.1 (M+), 181.1 (M+-CH3).

Compound 4k: Yield 91%; Light yellow liquid, dH (400 MHz, CDCl3) 0.24 (s, 9H), 1.0-2.0 (m, 16H).); dC (100.5 MHz, CDCl3) 1.26, 26.11, 26.13, 29.73, 34.09, 34.18, 34.30, 50.29, 69.03, 122.57. MS (EI), m/z 239.3 (M+), 223.5 (M+-CH3).

This Article

  1. Published online before print February 22, 2007, doi: 10.1073/pnas.0611309104 PNAS February 27, 2007 vol. 104 no. 9 3026-3030
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