LETTER
Propylphosphonic Anhydride
3381
spect to other reports and can be used as a valid
alternative, thus avoiding tedious purifications or the use
of more toxic reagents. This new procedure offers simple
and easily reproducible technique for nitrile synthesis and
highlights the synthetic utility of T3P as a versatile re-
agent in organic chemistry.
Table 5 Conversion of Aliphatic Aldehydes into Nitriles Promoted
by T3P
Entry Aldehyde
Product
Yield
(%)a
CN
CHO
1
91
23
Supporting Information for this article is available online at
CN
CHO
2
94
24
25
Acknowledgment
CN
CHO
3
93b
95
We thank Dr. Ashis Baran Mandal and gratefully acknowledge Dr.
Goutam Das, COO, Syngene International Ltd., for his precious
support.
CN
CHO
4
5
6
References and Notes
26
27
(1) Sandier, S. R.; Karo, W. In Organic Functional Group
Preparations, Vol. 12-I; Academic Press: San Diego, 1983,
Chap. 17.
(2) (a) Mowry, D. T. Chem. Rev. 1948, 42, 250. (b) Friedrich,
K.; Wallensfels, K. In The Chemistry of the Cyano Group;
Rappoport, Z., Ed.; Wiley-Interscience: New York, 1970.
(c) North, M. In Comprehensive Organic Functional Group
Transformations; Katrizky, A. R.; Meth-Cohn, O.; Rees,
C. W., Eds.; Pergamon: Oxford, 1995, 617.
97
94
CN
CHO
CN
CHO
S
S
28
(3) (a) Katritzky, A. R.; Zhang, G. F.; Fan, W. Q. Org. Prep.
Proced. Int. 1993, 25, 315. (b) Forey, H. G.; Datlon, D. R.
J. Chem. Soc., Chem. Commun. 1973, 628. (c) Kukhar,
V. P.; Pasternak, V. I. Synthesis 1974, 563. (d) Shinozaki,
H.; Imaizumi, M.; Tajima, M. Chem. Lett. 1983, 929.
(e) Meshram, H. M. Synthesis 1992, 943. (f) Findlay, J. A.;
Tang, C. S. Can. J. Chem. 1967, 45, 1014.
CN
7
85c
+
CHO
O
N
(4) (a) Brackman, W.; Smit, P. J. Recl. Trav. Chim. 1963, 82,
757. (b) Sato, R.; Itoh, Y.; Itep, K.; Nihina, H.; Goto, T.;
Saito, M. Chem. Lett. 1984, 1913. (c) Erman, M. B.; Snow,
J. W.; Williams, M. J. Tetrahedron Lett. 2000, 41, 6749.
(d) Talukdar, S.; Hsu, J. L.; Chou, T. C.; Fang, J. M.
Tetrahedron Lett. 2001, 42, 1103. (e) Bandgar, B. P.;
Makone, S. S. Synth. Commun. 2006, 36, 1347.
(5) (a) Karmarkar, S. N.; Kelkar, S. L.; Wadia, M. S. Synthesis
1985, 510. (b) Blatter, H. M.; Lukaszewski, H.; de Stevens,
G. J. Am. Chem. Soc. 1961, 83, 2203. (c) Olah, G. A.;
Keumi, T. Synthesis 1979, 112; and references cited therein.
(d) Dauzonne, D.; Demerseman, P.; Royer, R. Synthesis
1981, 739. (e) Saednya, A. Synthesis 1982, 190.
29
CN
CHO
8
9
94
95
O2N
O2N
30
CN
CHO
31
CN
CHO
93d
O
N
10
O
N
(f) Ganboa, I.; Palomo, C. Synth. Commun. 1983, 13, 219.
(g) Capdevielle, P.; Lavigne, A.; Maumy, M. Synthesis
1989, 451. (h) Bose, D. S.; Narsaiah, A. V. Tetrahedron
Lett. 1998, 39, 6533. (i) Kumar, H. M. S.; Reddy, B. V. S.;
Reddy, P. T.; Yadav, J. S. Synthesis 1999, 586.
O
O
32
a Isolated yields.
b Product is highly volatile and extracted with pentane.
c Separated by chromatography.
(6) (a) Wissmann, H.; Kleiner, H.-J. Angew. Chem., Int. Ed.
Engl. 1980, 19, 133. (b) Escher, R.; Bünning, P. Angew.
Chem., Int. Ed. Engl. 1986, 25, 277.
d Conditions: 3.0 equiv of base were used.
(7) For a brief review of the reagent, see: (a) Llanes García, A.
L. Synlett 2007, 1328. (b) Schwarz, M. Synlett 2000, 1369.
(8) Meudt, A.; Scherer, S.; Nerdinger, S. WO 2005070879,
2005; Chem. Abstr. 2005, 143, 172649.
into nitrile under conditions of electrophilic activation of
the oxime hydroxy group to form the phosphonate inter-
mediate, thus making it a better leaving group.
(9) Holla, W.; Napierski, B.; Rebenstock, H.-P. DE 19802969,
1999; Chem. Abstr. 1999, 131, 131507.
(10) Meudt, A.; Scherer, S.; Böhm, C. WO 2005123632, 2005;
Chem. Abstr. 2005, 144, 69544.
In summary, T3P has been demonstrated to be a remark-
ably efficient reagent for the one-pot access to aromatic,
heteroaromatic, and aliphatic nitriles from respective al-
dehydes.14 The method seems to be convenient with re-
Synlett 2009, No. 20, 3378–3382 © Thieme Stuttgart · New York