LETTER
Room-Temperature Condensation to Form a-Aminonitriles
805
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Acknowledgment
We are grateful to Basic Sciences Research Program (No.
06KJB530035) of Universities of Jiangsu Province, China, and the
Major Basic R&D Program of China (No. 2003CB716004) for
financial support.
References and Notes
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unit price of the least expensive catalyst Lewis acid in ref. 9,
12/2006).
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(21) General Experimental Procedure.
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A mixture of aldehyde (2.0 mmol), amine (2.0 mmol) and
sulfamic acid (20 mg) in MeCN (5.0 mL) was stirred at r.t.
for 20 min and then trimethylsilyl cyanide (1.6 mL, 2.4
mmol) was added. The resulting reaction mixture was stirred
at r.t. for the appropriate time. After completion of the
reaction (TLC, hexane–EtOAc = 1:5), sulfamic acid was
filtered off, the filtrate was extracted with EtOAc (3 × 10
mL), the combined organic phase was washed with H2O (20
mL) and sat. aq NH4Cl (20 mL), dried over anhyd MgSO4
and concentrated in vacuo to give the crude product, which
was purified by silica gel column chromatography (hexane–
EtOAc = 1: 3) to afford the pure 3a–v, all of which were
thoroughly characterized.
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Spectral Data of Representative Compounds.
2-(o-Toluidino)-2-phenylacetonitrile (3b): pale yellow solid;
mp 71–72 [lit.9e 72–73] °C. IR (KBr): 3365, 2237 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.20 (s, 3 H), 3.38 (br d,
J = 8.1 Hz,1 H, NH), 5.45 (d, J = 8.1 Hz, 1 H), 6.80 (t, J =
7.9 Hz, 2 H), 7.10 (d, J = 8.0 Hz, 1 H), 7.20 (d, J = 7.9 Hz, 1
H), 7.40–7.50 (m, 3 H), 7.50 (d, J = 8.0 Hz, 2 H). ESI-
HRMS: m/z calcd for C15H15N2+ [M + H]+: 223.1235; found:
223.1231.
2-Phenyl-2-(pyrrolidin-1-yl)acetonitrile (3l): colorless oil.
IR (neat): 2223 cm–1. 1H NMR (300 MHz, CDCl3): d = 1.75
(m, 4 H), 2.71–2.58 (m, 4 H), 5.03 (s, 1 H), 7.43–7.31 (m, 3
+
H), 7.53–7.49 (m, 2 H). ESI-HRMS: m/z calcd for C12H15N2
[M+H]+: 187.1235; found: 187.1237.
2-(Benzylamino)-2-(3-methoxyphenyl)acetonitrile (3r):
colorless oil. IR (neat): 3323, 2243 cm–1. 1H NMR (300
MHz, CDCl3): d = 1.84 (br s, 1 H), 3.77 (s, 3 H), 3.94 (q,
J = 13.0 Hz, 2 H), 4.66 (s, 1 H), 6.86 (dd, J = 2.5, 9.4 Hz, 1
H), 7.23 (m, 2H), 7.83–7.29 (m, 6 H). ESI-HRMS: m/z calcd
for C16H17N2O+ [M + H]+: 253.1341; found: 253.1338.
2-(Benzylamino)-3-methylbutanenitrile (3v): colorless oil.
IR (neat): 3347, 2228 cm–1. 1H NMR (300 MHz, CDCl3):
d = 1.07 (d, J = 6.7 Hz, 3 H), 1.08 (d, J = 6.8 Hz, 3 H), 1.55
(br s, 1 H), 1.98 (m, 1 H), 3.25 (d, J = 6.0 Hz, 1 H), 3.79 (d,
J = 13.0 Hz, 1 H), 4.06 (d, J = 13.0 Hz, 1 H), 7.36–7.23 (m,
5 H). ESI-HRMS: m/z calcd for C12H17N2+ [M + H]+:
189.1392; found: 189.1390.
(c) Matsumoto, K.; Kim, J. C.; Hayashi, N.; Jenner, G.
Tetrahedron Lett. 2002, 43, 9167.
Synlett 2007, No. 5, 803–805 © Thieme Stuttgart · New York