SHORT PAPER
References
Use of PyBOP as a Convenient Activator for the Synthesis of Nitriles from Primary Amides
375
(14) (a) Borch, R. F. Tetrahedron Lett. 1968, 61.
(b) Heck, M. P.; Wagner, A.; Mioskowski, C. J. Org. Chem.
1996, 61, 6486.
(c) Hendrickson, J. B.; Schwartzman, S. M. Tetrahedron Lett.
1975, 277.
(d) McElvain, S. M.; Clarke, R. L. J. Am. Chem. Soc. 1947, 69,
2657.
† IICT Communication No. 4384.
(1) (a) Paquette, L. A. Encyclopedia of Reagents for Organic
Synthesis; Wiley: Chichester, 1995; Vol. 1, pp 301 304.
(b) Coste, J.; Le-Nguyen, D.; Castro, B. Tetrahedron Lett.
1990, 31, 205.
(2) Coste J.; Campagne, J-M. Tetrahedron Lett. 1995, 36, 4253.
(3) (a) Friedrich, K.; Wallensfels, K. In The Chemistry of Cyano
Group; Rappoport, Z., Ed.; Wiley-Interscience: New York,
1970.
(b) Mowry, D. T. Chem. Rev. 1948, 42, 250.
(4) Chihiro, M.; Nagamoto, H.; Takemura, I.; Kitano, K.;
Komatsu, H.; Sekiguchi, K.; Tabusa, F.; Mori, T.; Tominnaga,
M.; Yabuuchi, Y. J. Med. Chem. 1995, 38, 353.
(5) Khanna, I. K.; Weier, R. M.; Yu, Y.; Xu, X. D.; Koszyk, F. J.;
Collins, P. W.; Koboldt, C. M.; Veenhuizen, A. W.; Perkins,
W. E.; Casler, J. J.; Masferrer, J. L.; Zhang, Y. Y.; Gregory, S.
A.; Seibert, K.; Isakson, P. C.; J. Med. Chem. 1997, 40, 1634.
(6) Medwid, J. B.; Paul, R.; Baker, J. S.; Brockman, J. A.; Du, M.
T.; Hallet, W. A.; Hanifin, J. W.; Hardy, R. A.; Tarrant, M. E.;
Torely, I. W.; Wrenn, S. J. Med. Chem. 1990, 33, 1230.
(7) (a) Fatiadi, A. J. The Chemistry of Triple-Bonded Funtional
Group Part 2; Patai, S.; Rappoport, Z., Eds.; Wiley: New
York, 1983, pp 1057.
(15) (a) Bose, D. S.; Srinivas, P. Synlett 1998, 977.
(b) Bose, D. S.; Lakshminarayana, V. Tetrahedron Lett. 1998,
39, 5631.
(c) Bose, D. S.; Jayalakshmi, B.; Venkat Narsaiah, A.
Synthesis 2000, 67.
(16) Physical and spectral data of compounds 2a c:
2a
IR (neat): = 3050 2830, 2230, 1600, 1550, 1490, 1400
1
cm .
1H NMR (CDCl3): = 8.65 (d, 1 H, J = 5 Hz), 7.31 7.29 (m,
2 H), 2.95 2.79 (q, 2 H, J = 8.5 Hz), 1.35 1.27 (t, 3 H, J = 8.5
Hz).
MS: m/z = 132 (M+).
2b
1
IR (KBr): = 2240, 1600, 1260, 830 cm .
1H NMR (200 MHz, CDCl3): = 7.42 (d, 1H, J = 8.4 Hz),
6.52 6.39 (m, 2 H), 3.86 (s, 3 H), 3.82 (s, 3 H).
MS: m/z = 163 (M+), 138, 103, 31.
(b) Stevens, T. E. J. Org. Chem. 1961, 26, 2531.
(c) Pakusch, J.; Ruchardt, C. Chem. Ber. 1991, 124, 971.
(8) (a) Patai, S. In The Chemistry of Functional Groups: Amides;
Zabicky, J., Ed.; Wiley: New York, 1970.
(b) Larock, R. C. Comprehensive Organic Transformations,
VCH: New York, 1989.
(9) (a) Reisner, D. B.; Coring, E. C. Org. Synth. Coll. Vol. IV
1963, 144.
2c
Mp 58 60 °C.
1
IR (KBr): = 2239 cm .
1H NMR (200 MHz, CDCl3): = 3.88 (s, 3 H, OCH3), 4.64
(dd, Jvicinal = 5.4, J4-bond = 1.2 Hz, 2 H, allylic H), 5.33 (ddd,
J
cis = 10.6, Jgem = 3.0, J4-bond = 1.2 Hz, 1 H, terminal vinylic H),
5.42 (ddd, Jtrans = 17.2, Jgem = 3.0, J4-bond 1.2 Hz, 1 H, terminal
vinylic H), 6.02 (m, 1 H, internal vinylic H), 6.90 (d,
(b) Lehnert, W. Tetrahedron Lett. 1971, 1501.
(c) Krynitsy, J. A.; Carhart, H. W. Org. Synth. Coll. Vol. IV
1963, 436.
(d) Campagna, F.; Carroti, A; Casini, G. Tetrahedron Lett.
1977, 1813.
J
ortho = 8.4 Hz, 1 H, Ar-H), 7.09 (d, Jmeta = 2.0 Hz, 1 H, Ar-H),
7.25 (dd, Jortho = 8.4, Jmeta = 2.0 Hz, 1 H, Ar-H).
The optical rotation of the product 2e indicated that no racemi-
zation had occurred during the transformation process; this
was confirmed by comparison with the amine hydrochloride
salt; [ ]D +30.0 (c = 1.0, H2O); Lit.17 [ ]D +33.0 (c = 1.001,
H2O).
(10) (a) Olah, G. A.; Narang, S. C.; Fung, A. P.; Gupta, B. C. G.
Synthesis 1980, 657.
(b) Bose, D. S.; Goud, P. R. Tetrahedron Lett. 1999, 40, 747.
(c) Bose, D. S.; Kiran Kumar, K. Synth. Commun. 2000, 30,
3047.
(17) Effenberger, F.; Kremser, A.; Stelzer, U. Tetrahedron:
Asymm. 1996, 7, 607
(11) Sznaidman, M. L.; Crasto, C.; Hecht, S. M. Tetrahedron Lett.
1993, 34, 1581.
(12) Campagna, F.; Carroti, A.; Casini, G. Tetrahedron Lett. 1977,
21, 1813.
Article Identifier:
1437-210X,E;2001,0,03,0373,0375,ftx,en;Z09500SS.pdf
(13) Correia, J. Synthesis 1994, 1127.
Synthesis 2001, No. 3, 373–375 ISSN 0039-7881 © Thieme Stuttgart · New York