D. Basavaiah et al. / Tetrahedron Letters 47 (2006) 5771–5774
5773
H
O
O
H
Ar
H
O
O
O
O
H
NH
H
+
Ar
Ar
H
Ar
OH
Ar
H
N
N
OH
O
OH
Ar
O
H N
2
N
+
Ar
H
H
N
Scheme 3. Plausible mechanism for the Cannizzaro reaction.
References and notes
Table 2. Formation of pyridin-4-ylmethanol 3a via the cross-Canniz-
zaro reaction
a,b
1
2
. (a) Seayad, J.; List, B. Org. Biomol. Chem. 2005, 3, 719–
724; (b) Suri, J. T.; Ramachary, D. B.; Barbas, C. F., III.
Org. Lett. 2005, 7, 1383–1385; (c) List, B. Tetrahedron
CHO
CH OH
2
O
TMG (1 eq.), rt
+
2
002, 58, 5573–5590; (d) Paras, N. A.; MacMillan, D. W.
H
H
H O, 4-7 h
N
2
C. J. Am. Chem. Soc. 2001, 123, 4370–4371.
N
. (a) March, J. Advanced Organic Chemistry, 4th ed.; John
Wiley Sons: New York, 1992; pp 1233–1235; (b) Compre-
hensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.;
Pergamon Press: New York, 1991; Vol. 8, p 86; (c)
Cannizzaro, S. Annuals 1853, 88, 129–130; (d) Geissman,
T. A. Org. React. 1944, II, 94–113.
1
a
3a
c
Entry
HCHO (equiv)
Time (h)
Yield (3a) (%)
1
2
3
4
5
1
2
4
4
4
4
4
7
50
56
60
60
64
3
. (a) Abaee, M. S.; Sharifi, R.; Mojtahedi, M. M. Org. Lett.
8
2
005, 7, 5893–5895; (b) Curini, M.; Epifano, F.; Genovese,
S.; Marcotullio, M. C.; Rosati, O. Org. Lett. 2005, 7,
331–1333; (c) Vida, Y.; Perez-Inestrosa, E.; Suau, R.
16
a
b
c
All the reactions were carried out on 2 mM of aldehyde 1a using
,1,3,3-tetramethylguanidine (2 mM) in water (0.5 mL) at room
temperature.
1
1
Tetrahedron Lett. 2005, 46, 1575–1577.
4
. (a) Rzepa, H. S.; Miller, J. J. Chem. Soc., Perkin Trans. 2
The alcohol was obtained in all the cases as a colorless solid and gave
1
985, 717–723; (b) Ashby, E. C.; Coleman, D. T., III;
1
13
satisfactory IR, H NMR (200 or 400 MHz) and C NMR (50 or
00 MHz) spectral data.
Isolated yields of the pure alcohol after column chromatography
silica gel, 100% EtOAc).
Gamasa, M. P. Tetrahedron Lett. 1983, 24, 851–854; (c)
Chung, S. K. J. Chem. Soc., Chem. Commun. 1982, 480–
1
4
82; (d) Swain, C. G.; Powell, A. L.; Sheppard, W. A.;
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583.
(
3
5
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of HCHO and found that a maximum yield (64%) of the
desired alcohol 3a could be obtained with 16 equiv of
HCHO (Table 2, entry 5).
6
7
8
. Russell, A. E.; Miller, S. P.; Morken, J. P. J. Org. Chem.
2
000, 65, 8381–8383.
. Bianchi, M.; Matteoli, U.; Menchi, G.; Frediani, P.;
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In conclusion, we have described for the first time an
organo-base (TMG) promoted Cannizzaro reaction.
Although this reaction is applicable only to reactive aro-
matic aldehydes, this work provides new perspectives
and avenues for further understanding the applications
of the Cannizzaro reaction.
9. (a) Yoshizawa, K.; Toyota, S.; Toda, F. Tetrahedron Lett.
2001, 42, 7983–7985; (b) Varma, R. S.; Naicker, K. P.;
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1
1
1. For reviews on the Baylis–Hillman reaction, see: (a)
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Acknowledgements
2
01–350; (c) Basavaiah, D.; Dharma Rao, P.; Suguna
We thank DST (New Delhi) for funding this project. We
thank UGC (New Delhi) for recognizing the University
of Hyderabad as a ‘University with Potential for Excel-
lence’ (UPE) and also recognizing our School of Chem-
istry as a Center for Advanced Studies in Chemistry and
providing some instrumental facilities. D.S.S. thanks
UGC and DST (New Delhi) and A.V. thanks CSIR
Hyma, R. Tetrahedron 1996, 52, 8001–8062; (d) Drewes, S.
E.; Roos, G. H. P. Tetrahedron 1988, 44, 4653–4670.
2. Phenyl vinyl sulfoxide requires a high pressure to undergo
Baylis–Hillman reaction with aldehydes. See: Ando, D.;
Bevan, C.; Brown, J. M.; Price, D. W. J. Chem. Soc.,
Chem. Commun. 1992, 592–594.
1
13. For Baylis–Hillman reactions in dioxane/water medium,
(
New Delhi) for their research fellowships.
see: (a) Yu, C.; Hu, L. J. Org. Chem. 2002, 67, 219–223;