Rhodium (Chief Bee)
03-17-03 01:22
No 417771
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Homologation of arylaldehydes to arylacetonitriles
Tetrahedron Letters 44(14), 2903-2905 (2003)


Treatment of heteroaryl-aldehydes with diethyl cyanophosphonate in the presence of a catalytic amount of LiCN affords phosphorylated cyanohydrins which are reduced in situ with SmI2 to give heteroaryl-acetonitriles in generally good overall yields (50–100%). The generality of the process is demonstrated.

Other methods for direct homologation of arylaldehydes to arylacetonitriles:

(a) van Leusen, A. M.; Oomkes, P. G. Synth. Commun. 1980, 10, 399–403;
(b) Schöllkopf, U.; Schröder, R. Angew. Chem., Int. Ed. Engl. 1973, 12, 407–408;
(c) Santiago, B.; Meyers, A. I. Tetrahedron Lett. 1993, 34, 5839–5842.

For selected methods that have been applied to aliphatic/alicyclic aldehydes but either fail or proceed in low yield for aromatic aldehydes, or have not been applied to aryl aldehydes, see:

(d) Jiricny, J.; Orere, D. M.; Reese, C. B. J. Chem. Soc., Perkin Trans. 1 1980, 1487–1492;
(e) Nicolaou, K. C.; Vassilikogiannakis, G.; Kranich, R.; Baran, P. S.; Zhong, Y.-L.; Natarajan, S. Org. Lett. 2000, 2, 1895–1898;
(f) Kloubert, S.; Mathé-Allainmat, M.; Andrieux, J.; Langlois, M. Synth. Commun. 2000, 30, 2873–2887;
(g) Kamogawa, H.; Kanzawa, A.; Kadoya, M.; Naito, T.; Nanasawa, M. Bull. Chem. Soc. Jpn. 1983, 56, 762–765;
(h) Yokoyama, M.; Ohteki, H.; Kurauchi, M.; Hoshi, K.; Yanagisawa, E.; Suzuki, A.; Imamoto, T. J. Chem. Soc., Perkin Trans. 1 1984, 2635–2640.