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X. Wang, S.-K. Tian
LETTER
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(11) Most of the neutral p-nucleophiles listed in Table 1 are
electron-rich substituted enol ethers. However, electron-rich
enamines and the silyl enol derivatives of amides are
excluded from the survey since they react readily with
aldehydes at r.t. For the silyl enol derivatives of amides, see:
Myers, A. G.; Widdowson, K. L. J. Am. Chem. Soc. 1990,
113, 9672.
(12) General Procedure
A mixture of aldehyde or ketone 1a–s (0.50 mmol), TMSCN
(0.60–0.75 mmol) and catalyst 3j (1–15 mol%) was allowed
to stand in a vial at 16–50 °C (indicated in Table 2). The
reaction was monitored by GC or TLC. After the aldehyde
or ketone was completely consumed, the reaction mixture
was subject to a reduced pressure of 5–10 mmHg at 25–50
°C to remove catalyst 3j and the remaining TMSCN, and the
desired product 2a–s was obtained in quantitative yield.
Cyanohydrin silyl ethers 2a–s are known compounds, see
ref. 8–10.
(13) The boiling point of catalyst 3j is 57 °C/15 mmHg, and that
of TMSCN is 118 °C.
(9) For the organocatalysis using alkyl cyanoformate as a
cyanide source, see: (a) Berthiaume, D.; Poirier, D.
Tetrahedron 2000, 56, 5995. (b) Deardorff, D. R.;
Taniguchi, C. M.; Tafti, S. A.; Kim, H. Y.; Choi, S. Y.;
Downey, K. J.; Nguyen, T. V. J. Org. Chem. 2001, 66,
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6195. (d) Tian, S.-K.; Deng, L. Tetrahedron 2006, 62,
11320. (e) Poirier, D.; Berthiaume, D.; Boivin, R. P. Synlett
1999, 1423.
(10) For some other recent examples, see: (a) Xiong, Y.; Huang,
X.; Gou, S.; Huang, J.; Wen, Y.; Feng, X. Adv. Synth. Catal.
2006, 348, 538. (b) Iwanami, K.; Aoyagi, M.; Oriyama, T.
Tetrahedron Lett. 2006, 47, 4741. (c) Li, Q.; Liu, X.; Wang,
J.; Shen, K.; Feng, X. Tetrahedron Lett. 2006, 47, 4011.
(d) Khan, N. H.; Agrawal, S.; Kureshy, R. I.; Abdi, S. H. R.;
Mayani, V. J.; Jasra, R. V. Tetrahedron: Asymmetry 2006,
(14) For previously reported methods, the extractive procedures
and/or column chromatography are needed to purify the
products. See references 7–10, and references cited therein.
(15) For a review on silicon Lewis acid catalysis, see: Dilman, A.
D.; Ioffe, S. L. Chem. Rev. 2003, 103, 733.
(16) For the IR study on the activation of TMSCN with
nucleophilic Ph3PO, see: Ryu, D. H.; Corey, E. J. J. Am.
Chem. Soc. 2004, 126, 8106. For IR spectral data on
TMSCN and TMSNC, see: Seckar, J. A.; Thayer, J. S. Inorg.
Chem. 1976, 15, 501.
(17) No significant IR change was observed for benzaldehyde (or
ethyl cyanoformate) with the addition of catalyst 3j.
(18) Based on its p-nucleophilicity, we speculate that catalyst 3j
may activate the cyanating agent with its p-system through
association. However, to our knowledge, this type of p-
based catalysis has not been reported previously.
Synlett 2007, No. 9, 1416–1420 © Thieme Stuttgart · New York