PAPER
One-Pot Conversion of Alcohols into Nitriles
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.
2163
Dec-9-enenitrile
Colorless oil; yield: 299.5 mg (99%).
–
1
IR (neat): 2245 cm .
1
H NMR (400 MHz, CDCl ): δ = 1.25–1.45 (m, 8 H), 1.66 (quint,
3
(
3) (a) Miller, C. S. Org. Synth., Coll. Vol. III; John Wiley &
Sons: London, 1955, 646. (b) Cope, A. C.; Cotter, R. J.;
Estes, L. L. Org. Synth., Coll. Vol. IV; John Wiley & Sons:
London, 1963, 62. (c) Imamoto, T.; Takaoka, ; Yokoyama,
M. Synthesis 1983, 142. (d) Larock, R. C. Comprehensive
Organic Transformations: A Guide to Functional Group
Preparations; VCH: New York, 1989, 976. For metal-
catalyzed dehydration, see: (e) Ishihara, K.; Furuya, Y.;
Yamamoto, H. Angew. Chem. Int. Ed. 2002, 41, 2983; and
references on metal-catalyzed dehydrations of amides cited
therein.
(4) (a) Clarke, T. G.; Hampson, N. A.; Lee, J. B.; Morley, J. R.;
Scanlon, B. Tetrahedron Lett. 1968, 5685. (b) Vargha, L.;
Remenyi, M. J. Chem. Soc. 1951, 1068. (c) Cason, J. Org.
Synth., Coll. Vol. III; John Wiley & Sons: London, 1955, 3.
(d) Mihailovic, M. L.; Stojiljkovic, A.; Andrejevic, V.
Tetrahedron Lett. 1965, 461. (e) Stojiljkovic, A.;
J = 7.4 Hz, 2 H), 2.05 (dtt, J = 7.0, 6.8, 1.5 Hz, 2 H), 2.33 (t, J = 7.4
Hz, 2 H), 4.94 (ddt, J = 10.4, 2.0, 1.5 Hz, 1 H), 5.00 (ddt, J = 17.0,
2.0, 1.5 Hz, 1 H), 5.80 (ddt, J = 10.4, 17.0, 7.0 Hz, 1 H).
13
C NMR (100 MHz, CDCl ): δ = 17.04, 25.27, 28.52, 28.65, 33.59,
3
114.27, 119.76, 138.83.
HRMS (ESI): m/z [M + H]+ calcd for C H N: 152.1434;
found: 152.1434.
1
0
18
2
-Methyl-2-phenylpropanenitrile
1
1
Colorless oil; yield: 284.6 mg (98%); (lit. oil).
–
1
IR (neat): 2237 cm .
1
H NMR (500 MHz, CDCl ): δ = 1.73 (s, 6 H), 7.31 (t, J = 7.3 Hz,
3
1
H), 7.39 (dd, J = 7.3, 8.0 Hz, 2 H), 7.48 (d, J = 8.0 Hz, 2 H).
13
C NMR (125 MHz, CDCl ): δ = 29.11, 37.11, 124.48, 125.00,
3
127.73, 128.88, 141.37.
Andrejevic, V.; Mihailovic, M. L. Tetrahedron 1967, 23,
1
-Methylcyclohexanecarbonitrile
721. (f) Below, J. S.; Garza, C.; Mathieson, J. W. J. Chem.
1
2
Colorless oil; yield: 243.9 mg (99%); (lit. oil).
Soc. D 1970, 634. (g) Nakagawa, K.; Tsuji, T. Chem. Pharm.
Bull. 1963, 11, 296. (h) Troyanskii, E. I.; Svitanko, I. V.;
Ioffe, V. A.; Nikishin, G. I. Izv. Akad. Nauk SSSR, Ser. Khim.
–
1
IR (neat): 2232 cm .
1
H NMR (400 MHz, CDCl ): δ = 1.08–1.27 (m, 3 H), 1.32 (s, 3 H),
3
1
982, 2180. (i) Yamazaki, S.; Yamazaki, Y. Bull. Chem.
1.53–1.76 (m, 5 H), 1.93 (d, J = 13.4 Hz, 2 H).
Soc. Jpn. 1990, 63, 301. (j) Biondini, D.; Brinchi, L.;
Germani, R.; Goracci, L.; Savelli, G. Eur. J. Org. Chem.
13
C NMR (100 MHz, CDCl ): δ = 23.15, 25.01, 27.35, 34.41, 37.25,
3
124.60.
2
005, 3060. (k) Chen, E.; Peng, Z.; Fu, H.; Liu, J.; Shao, L.
J. Chem. Res., Synop. 1999, 726. (l) Lee, G. A.; Freedman,
H. H. Tetrahedron Lett. 1976, 1641. (m) Yamazaki, S.
Synth. Commun. 1997, 27. (n) Jursic, B. J. Chem. Res.,
Synop. 1988, 168. (o) Nikishin, G. I.; Troyanskii, E. I.; Joffe,
V. A. Izv. Akad. Nauk SSSR, Ser. Khim. 1982, 2758.
(p) Kametani, T.; Takahashi, K.; Ohsawa, T.; Ihara, M.
Synthesis 1977, 245. (q) Capdevielle, P.; Lavigne, A.;
Maumy, M. Synthesis 1989, 453. (r) Capdevielle, P.;
Lavigne, A.; Sparfel, D.; Baranne-Lafont, J.; Nguyen, K. C.;
Maumy, M. Tetrahedron Lett. 1990, 31, 3305. (s) Maeda,
Y.; Nishimura, T.; Uemura, S. Bull. Chem. Soc. Jpn. 2003,
Acknowledgment
A Grant-in-Aid for Scientific Research (No. 25105710) from the
Ministry of Education, Culture, Sports, Science, and Technology of
Japan and financial aid from the Iodine Research Project at Chiba
University are gratefully acknowledged.
References
(1) (a) Friedrich, K.; Wallensfels, K. The Chemistry of the
7
6, 2399. (t) Tang, R.; Diamond, S. E.; Neary, N.; Mares, F.
Cyano Group; Rappoport, Z., Ed.; Interscience: London,
J. Chem. Soc., Chem. Commun. 1978, 562. (u) Schroder, M.;
Griffith, W. P. J. Chem. Soc., Chem. Commun. 1979, 58.
1
970, Chap. 2, 67. (b) North, M. In Comprehensive Organic
Functional Group Transformations; Katritzky, A. R.; Meth-
Cohn, O.; Rees, C. W., Eds.; Vol. 3; Pergamon: Oxford,
(
(
v) Bailey, A. J.; James, B. R. Chem. Commun. 1996, 2343.
w) Mori, K.; Yamaguchi, K.; Mizugaki, T.; Ebitani, K.;
1
995, Chap. 18, 611. (c) Murahashi, S.-I. In Science of
Synthesis; Vol. 19; Murahashi, S.-I., Ed.; Thieme: Stuttgart,
004, 345. (d) Collier, S. J.; Langer, P. In Science of
Synthesis; Vol. 19; Murahashi, S.-I., Ed.; Thieme: Stuttgart,
004, 403.
Kaneda, K. Chem. Commun. 2001, 461. (x) Yamaguchi, K.;
Mizuno, N. Angew. Chem. Int. Ed. 2003, 42, 1480.
2
(
y) Moriarty, R. M.; Vaid, R. K.; Duncan, M. P.; Ochiai, M.;
Inenaga, M.; Nagao, Y. Tetrahedron Lett. 1988, 29, 6913.
z) Chen, F.; Kuang, Y.; Dai, H.; Lu, L.; Huo, M. Synthesis
003, 2629.
5) (a) Yamazaki, S.; Yamazaki, Y. Chem. Lett. 1990, 571.
2
(
2
(
2) (a) Wipf, P. Chem. Rev. 1995, 95, 2115. (b) Wipf, P.;
Yokokawa, F. Tetrahedron Lett. 1998, 39, 2223. (c) Ducept,
P. C.; Marsden, S. P. Synlett 2000, 692. (d) Chihiro, M.;
Nagamoto, H.; Takemura, I.; Kitano, K.; Komatsu, H.;
Sekiguchi, K.; Tabusa, F.; Mori, T.; Tominaga, M.;
(
(
(
b) Chen, F.; Li, Y.; Xu, M.; Jia, H. Synthesis 2002, 1804.
c) McAllister, G. D.; Wilfred, C. D.; Taylor, R. J. K. Synlett
2
002, 1291. (d) Yamaguchi, K.; He, J.; Oishi, T.; Mizuno, N.
Yabuuchi, Y. J. Med. Chem. 1995, 38, 353. (e) Gu, X.-H.;
Wan, X.-Z.; Jiang, B. Bioorg. Med. Chem. Lett. 1999, 9, 569.
Chem. Eur. J. 2010, 16, 7199. (e) Ishida, T.; Watanabe, H.;
Takei, T.; Hamasaki, A.; Tokunaga, M.; Haruta, M. Appl.
Catal., A 2012, 425, 85. (f) Yin, W.; Wang, C.; Huang, Y.
Org. Lett. 2013, 15, 1850.
(f) Kadaba, P. K. Synthesis 1973, 71. (g) Diana, G. D.;
Cutcliffe, D.; Volkots, D. L.; Mallamo, J. P.; Bailey, T. R.;
Vescio, N.; Oglesby, R. C.; Nitz, T. J.; Wetzel, J.; Giranda,
V.; Pevear, D. C.; Dutko, F. J. J. Med. Chem. 1993, 36, 3240.
(
6) (a) Mori, N.; Togo, H. Synlett 2005, 1456. (b) Iida, S.; Togo,
H. Tetrahedron 2007, 63, 8274.
7) (a) Mori, N.; Togo, H. Synlett 2004, 880. (b) Mori, N.; Togo,
H. Tetrahedron 2005, 61, 5915. (c) Ishihara, M.; Togo, H.
Synlett 2006, 227. (d) Iida, S.; Togo, H. Synlett 2006, 2633.
(h) Wittenberger, S. J.; Donner, B. G. J. Org. Chem. 1993,
(
5
8, 4139. (i) Shie, J.-J.; Fang, J.-M. J. Org. Chem. 2003, 68,
1
158. (j) Medwid, J. B.; Paul, R.; Baker, J. S.; Brockman, J.
A.; Du, M. T.; Hallett, W. A.; Hanifin, J. W.; Hardy, R. A.
Jr; Tarrant, M. E.; Torley, L. W.; Wrenn, S. J. Med. Chem.
(
(
e) Ishihara, M.; Togo, H. Tetrahedron 2007, 63, 1474.
f) Iida, S.; Togo, H. Synlett 2007, 407. (g) Iida, S.; Togo, H.
1
990, 33, 1230. (k) Khanna, I. K.; Weier, R. M.; Yu, Y.; Xu,
©
Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 2155–2164