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Gold(III)-Catalyzed Cyanosilylation of Ketones and Aldehydes
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1-(Trimethylsiloxy)cyclopentanecarbonitrile (Table 1, entry 1)
1H NMR (400 MHz, CDCl3): d = 0.21 (s, 9 H), 1.70–1.85 (m, 4 H),
1.90–1.99 (m, 2 H), 2.07–2.15 (m, 2 H).
2-Methyl-2-(trimethylsiloxy)pentanenitrile (Table 1, entry 10)
1H NMR (400 MHz, CDCl3): d = 0.21 (s, 9 H), 0.94 (t, J = 7.20 Hz,
3 H), 1.37–1.63 (m, 5 H), 1.64–1.75 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 1.09, 22.62, 41.73, 74.47, 122.63.
13C NMR (100 MHz, CDCl3): d = 1.27, 13.79, 17.65, 28.92, 45.50,
69.59, 122.20.
MS (EI): m/z calcd for C9H17NOSi: 183.11; found: 183.05.
MS (EI): m/z calcd for C9H19NOSi: 185.12; found: 185.13.
4-Methyl-1-(trimethylsiloxy)cyclohexanecarbonitrile (Table 1,
entry 3)
2-Methyl-2-(trimethylsiloxy)but-3-enenitrile (Table 1, entry 11)
1H NMR (400 MHz, CDCl3): d = 0.21 (s, 9 H), 1.62 (s, 3 H), 5.23–
5.86 (m, 3 H).
13C NMR (100 MHz, CDCl3): d = 1.30, 30.44, 70.12, 115.88,
120.46, 138.74.
1H NMR (400 MHz, CDCl3): d = 0.21 (s, 9 H), 0.88–0.92 (m, 3 H),
1.20–1.40 (m, 3 H), 1.52–1.55 (m, 2 H), 1.70–1.73 (m, 2 H), 1.95–
2.13 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 1.21, 1.50, 21.48, 28.58, 31.21,
31.73, 39.45, 71.49, 121.72.
MS (EI): m/z calcd for C8H15NOSi: 169.09; found: 169.06.
MS (EI): m/z calcd for C11H21NOSi: 211.14; found: 211.05.
Acknowledgment
1-(Trimethylsiloxy)cyclohex-2-enecarbonitrile (Table 1, entry
4)
This work was supported by the Korea Science and Engineering
Foundation (KOSEF) through the Center for Molecular Design and
Synthesis (CMDS) and a Korea Research Foundation grant funded
by the Korea Government (MOEHRD, Basic Research Promotion
Fund; KRF-2005-070-C00078).
1H NMR (400 MHz, CDCl3): d = 0.22 (s, 9 H), 1.76–1.80 (m, 2 H),
1.88–2.15 (m, 4 H), 5.71–5.74 (m, 1 H), 5.92–5.96 (m, 1 H).
13C NMR (100 MHz, CDCl3): d = 1.50, 18.35, 24.29, 36.93, 66.80,
121.86, 127.62, 132.58.
MS (EI): m/z calcd for C10H17NOSi: 195.11; found: 194.99.
References
2-Phenyl-2-(trimethylsiloxy)propanenitrile (Table 1, entry 5)
1H NMR (400 MHz, CDCl3): d = 0.15 (s, 9 H), 1.84 (s, 3 H), 7.34–
7.38 (m, 3 H), 7.51–7.54 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 1.05, 33.56, 71.61, 121.64,
124.61, 128.62, 128.64, 142.0.
(1) These authors contributed equally to this work.
(2) (a) Kruse, C. G. In Chirality in Industry; Collins, A. N.;
Sheldrake, G. N.; Crosby, J., Eds.; Wiley: Chichester, 1992,
Chap. 14. (b) Andrés, J. M.; Martínez, M. A.; Pedrosa, R.;
Pérez-Encabo, A. Tetrahedron: Asymmetry 2001, 12, 347.
(c) Gregory, R. J. H. Chem. Rev. 1999, 99, 3649.
MS (EI): m/z calcd for C12H17NOSi: 219.11; found: 220.06.
(3) Prakash, G. K. S.; Vaghoo, H.; Panja, C.; Surampudi, V.;
Kultyshev, R.; Mathew, T.; Olah, G. A. Proc. Natl. Acad.
Sci. U.S.A. 2007, 104, 3026.
2-(4-Tolyl)-2-(trimethylsiloxy)propanenitrile (Table 1, entry 6)
1H NMR (400 MHz, CDCl3): d = 0.15 (s, 9 H), 1.82 (s, 3 H), 2.34
(s, 3 H), 7.16–7.18 (m, 2 H), 7.39–7.41 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 1.06, 21.05, 33.51, 71.51, 121.76,
124.58, 129.24, 138.52, 139.08.
(4) (a) Liang, S.; Bu, X. R. J. Org. Chem. 2002, 67, 2702.
(b) You, J.-S.; Gau, H.-M.; Choi, M. C. K. Chem. Commun.
2000, 1963. (c) Iovel, I.; Popelis, Y.; Fleisher, M.; Lukevics,
E. Tetrahedron: Asymmetry 1997, 8, 1279. (d) Bandini, M.;
Cozzi, P. G.; Garelli, A.; Melchiorre, P.; Umani-Ronchi, A.
Eur. J. Org. Chem. 2002, 3243. (e) Jenner, G. Tetrahedron
Lett. 1999, 40, 491. (f) Saravanan, P.; Anand, R. V.; Singh,
V. K. Tetrahedron Lett. 1998, 39, 3823. (g) Karimi, B.;
MáMani, L. Org. Lett. 2004, 6, 4813.
MS (EI): m/z calcd for C13H19NOSi: 233.12; found: 233.03.
2-(4-Methoxyphenyl)-2-(trimethylsiloxy)propanenitrile (Table
1, entry 7)
1H NMR (400 MHz, CDCl3): d = 0.14 (s, 9 H), 1.82 (s, 3 H), 3.80
(s, 3 H), 6.87–6.89 (m, 2 H), 7.43–7.45 (m, 2 H).
(5) (a) Wang, L.; Huang, X.; Jiang, J.; Liu, X.; Feng, X.
Tetrahedron Lett. 2006, 47, 1581. (b) Fetterly, B. M.;
Verkade, J. G. Tetrahedron Lett. 2005, 46, 8061.
13C NMR (100 MHz, CDCl3): d = 1.06, 33.41, 55.33, 71.26, 113.86,
121.79, 126.04, 134.04, 159.76.
(c) Ishikawa, T.; Isobe, T. Chem. Eur. J. 2002, 8, 552.
(d) Song, J. J.; Gallou, F.; Reeves, J. T.; Tan, Z.; Yee, N. K.;
Senanayake, C. H. J. Org. Chem. 2006, 71, 1273.
(e) Suzuki, Y.; Bakar, A.; Kazuyuki, M. D.; Muramatsu, K.;
Sato, M. Tetrahedron 2006, 62, 4227.
MS (EI): m/z calcd for C13H19NO2Si: 249.12; found: 249.14.
2-(4-Nitrophenyl)-2-(trimethylsiloxy)propanenitrile (Table 1,
entry 8)
1H NMR (400 MHz, CDCl3): d = 0.22 (s, 9 H), 1.85 (s, 3 H), 7.71
(d, J = 8.80 Hz, 2 H), 8.24 (d, J = 8.80 Hz, 2 H).
(6) (a) Xiong, Y.; Huang, X.; Gou, S.; Huang, J.; Wen, Y.; Feng,
X. Adv. Synth. Catal. 2006, 348, 538. (b) Shen, Y.; Feng,
X.; Li, Y.; Zhang, G.; Jiang, Y. Eur. J. Org. Chem. 2004,
129. (c) He, B.; Chen, F.-X.; Li, Y.; Feng, X.; Zhang, G.
Tetrahedron Lett. 2004, 45, 5465. (d) Tian, S.-K.; Hong, R.;
Deng, L. J. Am. Chem. Soc. 2003, 125, 9900.
13C NMR (100 MHz, CDCl3): d = 1.04, 33.45, 70.91, 120.62,
123.99, 125.71, 148.04, 148.95.
MS (EI): m/z calcd for C12H16NO3Si: 264.09; found: 264.11.
(7) (a) Yadav, J. S.; Reddy, B. V. S.; Reddy, M. S.; Prasad, A.
R. Tetrahedron Lett. 2002, 43, 9703. (b) Kruchok, I. S.;
Gerus, I. I.; Kukhar, V. P. Tetrahedron 2000, 56, 6533.
(8) (a) Wilkinson, H. S.; Grover, P. T.; Vandenbossche, C. P.;
Bakale, R. P.; Bhongle, N. N.; Wald, S. A.; Senanayake, C.
H. Org. Lett. 2001, 3, 553. (b) Yang, Z.; Zhou, Z.; He, K.;
Wang, L.; Zhao, G.; Zhou, Q.; Tang, C. Tetrahedron:
Asymmetry 2003, 14, 3937. (c) Suzuki, M.; Kato, N.; Kanai,
M.; Shibasaki, M. Org. Lett. 2005, 7, 2527.
Diphenyl(trimethylsiloxy)acetonitrile (Table 1, entry 9)
1H NMR (400 MHz, CDCl3): d = 0.12 (s, 9 H), 7.30–7.36 (m, 6 H),
7.47–7.50 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 0.91, 76.42, 120.71, 125.90,
128.55, 128.65, 141.95.
MS (EI): m/z calcd for C17H19NO3Si: 281.12; found: 281.27.
Synthesis 2008, No. 4, 507–510 © Thieme Stuttgart · New York