3424
M. Sridhar et al. / Tetrahedron Letters 53 (2012) 3421–3424
O
F3C
S
O
N
O
H
Bi(OTf)2
OH
H
R
OH
H
R
Bi(OTf)3
AHA
N
O
R-CN
Bi(OTf)3
2
3
1
R
[Bi(OTf)2OH + TfOH]
Bi(OTf)3 + H2O
Regeneration of the catalyst
Scheme 3. Plausible mechanism for formation of a nitrile from the reaction of an aldehyde with AHA under Bi(OTf)3 catalysis.
Table 4
Formation of a nitrile from an aldoxime under Bi(OTf)3 catalysis
NOH
Bi(OTf)3 (5 mol%)
CH3CN, reflux
R-CN
3
R
H
2
S. No.
Oxime 2
Reaction time (h)
Nitrile 3
% Yielda
3
S. No.
Oxime 2
Reaction time (h)
Nitrile 3
% Yielda
3
1
2
3
4
5
2a
2b
2c
2d
2k
6
8
6
6
8
3a
3b
3c
3d
3k
97
93
93
95
87
6
7
8
9
10
2n
2o
2s
2t
10
8
8
10
8
3n
3o
3s
3t
83
96
86
86
91
2v
3v
a
Isolated yields.
Tetrahedron Lett. 2009, 50, 1717–1719; (g) Malashikhin, S. A.; Baldridge, K. K.;
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This work also describes the first application of Bi(OTf)3 as the cat-
alyst for efficient conversion of aldoximes into nitriles.
Acknowledgements
K.K.R.M., R.J., C.R.B., K.R.G. are thankful to the CSIR, New Delhi
and N.C. is thankful to the UGC, New Delhi for the financial support
in the form of research fellowship.
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References and notes
13.
A typical method for preparation of nitrile from aldehyde using AHA: 4-
Isopropylbenzaldehyde 1a (0.50 g, 3.37 mmol), acetohydroxamic acid (0.30 g,
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chromatography(silica gel 100–200 mesh, ethyl acetate/hexane = 1:20) to
obtain 4-isopropylbenzonitrile 3a (0.47 g, 97%) in the form of a colorless
liquid and it was characterized by the following spectral data: 1H NMR
(300 MHz, CDCl3): d = 7.60–7.56 (d, J = 8.5 Hz, 2H), 7.33–7.30 (d, J = 8.7 Hz, 2H),
3.00–2.91 (q, J = 6.9 Hz, 1H), 1.27–1.25 (d, J = 6.8 Hz, 6H); 13C NMR (75 MHz,
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15. A typical method for preparation of a nitrile from an aldoxime using Bi(OTf)3 as the
catalyst: 4-Isopropylbenzaldoxime 2a (0.5 g, 3 mmol), Bi(OTf)3 (60 mg,
0.09 mmol) and acetonitrile (5 ml) were taken into a 25 ml round bottomed
flask fitted with a condenser and CaCl2 guard tube. The mixture was refluxed
and when reaction was complete (GC), the reaction mixture was cooled to
room temperature, concentrated under reduced pressure and the crude
product was purified by normal column chromatography (silica gel 100–200
mesh, EtOAc/hexane = 1:20) to obtain 4-isopropylbenzonitrile 3a (0.43 g, 97%),
which gave the spectral data identical to that given above.