2
684
A. B. Khemnar et al. / Tetrahedron Letters 54 (2013) 2682–2684
corresponding nitrile (Table 2, entries 2–5). 1-Iodonapthalene pro-
vides an excellent yield of 1-naphthonitrile (Table 2, entry 6). Aryl
halide bearing an electron withdrawing substituent provided lower
yield of expected product under present reaction conditions
5. Li, Z.; Chen, J.; Xu, H.; Hu, S.; Shen, D. Progress In Electromagnetics Research
Symposium (PIERS) Proceedings, Hangzhou, China, March 2008, 24-28.
6.
(a) Sundermeier, M.; Zapf, A.; Beller, M.; Sans, J. Tetrahedron Lett. 2001, 42,
707–6710; (b) Yang, C.; Williams, J. M. Org. Lett. 2004, 6, 2837–2840.
6
7. (a) Marcantonio, K. M.; Frey, L. F.; Liu, Y.; Chen, Y.; Strine, J.; Phenix, B.; Wallace,
D. J.; Chen, C. Org. Lett. 2004, 6, 3723–3725; (b) Yu, H.; Richey, R. N.; Miller, W.
D.; Xu, J.; May, S. A. J. Org. Chem. 2011, 76, 665–668.
(
Table 2, entry 7). Free amino group bearing substrate that is 4-iodo
aniline also gives 4-aminobenzonitrile product in moderate yield
Table 2, entry 8). Heterocyclic aryl iodide also works under
optimized reaction conditions and furnishes a moderate yield of
8.
a) Friedman, L.; Shechter, H. J. Org. Chem. 1960, 25, 877–879; b) Ushkov, A. V.;
Grushin, V. V. J. Am. Chem. Soc. 2011, 133, 10999–11005.
(
9.
(a) Schareina, T.; Zapf, A.; Beller, M. Tetrahedron Lett. 2005, 46, 2585–2588; (b)
Grossman, O.; Gelman, D. Org. Lett. 2006, 8, 1189–1191; (c) Velmathi, S.;
Leadbeater, N. E. Tetrahedron Lett. 2008, 49, 4693–4694; (d) Yeung, P. Y.; So, C.
M.; Lau, C. P.; Kwong, F. Y. Angew. Chem., Int. Ed. 2010, 49, 8918–8922; (e)
Yeung, P. Y.; Tsang, C. P.; Kwong, F. Y. Tetrahedron Lett. 2011, 52, 7038–7041.
1H-indole-5-carbonitrile (Table 2, entry 9).
It was observed that various aryl bromides also work under
optimized reaction conditions and furnish moderate to acceptable
yields of their corresponding nitrile product (Table 2, entries 10–
10. Ren, Y.; Dong, C.; Zhao, S.; Sun, Y.; Ma, J.; Hou, C.; Wang, J. Tetrahedron Lett.
2012, 53, 2825–2827.
1
4).
In conclusion, we have developed a non-toxic, convenient, and
11. (a) Tsuji, Y.; Kusui, T.; Kojima, T.; Sugiura, Y.; Yamada, N.; Tanaka, S.; Ebihara,
M.; Kawamura, T. Organometallics 1998, 17, 4835–4841; (b) Jin, F.; Confalone,
P. N. Tetrahedron Lett. 2000, 41, 3271–3273; (c) Cristau, H. J.; Ouali, A.; Spindler,
J. F.; Taillefer, M. Chem. Eur. J. 2005, 11, 2483–2492; (d) Schareina, T.; Zapf, A.;
Magerlein, W.; Muller, N.; Beller, M. Chem. Eur. J. 2007, 13, 6249–6254; (e) Ren,
Y.; Wang, W.; Zhao, S.; Tian, X.; Wang, J.; Yin, W.; Cheng, L. Tetrahedron Lett.
cyanide free protocol for cyanation of aryl halides. The developed
protocol proves to be an attractive alternative to the reported toxic
methods for nitrile synthesis. A variety of aryl halides containing
electron donating and withdrawing groups are also tolerated in
present reaction conditions.
2010, 51, 2669–2670.
1
2. (a) Sekiya, A.; Ishikawa, N. Chem. Lett. 1975, 277–278; (b) Sundermeier, M.;
Zapf, A.; Mutyala, S.; Baumann, W.; Sans, J.; Weiss, S.; Beller, M. Chem. Eur. J., in
press.; (c) Sundermeier, M.; Zapf, A.; Beller, M. Angew. Chem., Int. Ed. 2003, 42,
1661.
Acknowledgments
1
3. (a) Kim, J.; Chang, S. J. Am. Chem. Soc. 2010, 132, 10272–10274; (b) Zhang, G.;
Ren, X.; Chen, J.; Hu, M.; Cheng, J. Org. Lett. 2011, 13, 5004–5007; (c) Ding, S.;
Jiao, N. J. Am. Chem. Soc. 2011, 133, 12374–12377.
The author (A.B.K.) is greatly thankful to the Council of Scientific
and Industrial Research (CSIR) India for providing junior research
fellowship (JRF).
1
1
1
4. (a) Zhou, W.; Xu, J.; Zhang, L.; Jiao, N. Org. Lett. 2010, 12, 2888–2891; (b)
Rokade, B. V.; Prabhu, K. R. J. Org. Chem. 2012, 77, 5364–5370.
5. Sawant, D. N.; Wagh, Y. S.; Tambade, P. J.; Bhatte, K. D.; Bhanage, B. M. Adv.
Synth. Catal. 2011, 353, 781–787.
6. Typical experimental procedure:- in an oven dried 25 ml two-necked round-
bottom flask equipped with a condenser was placed a mixture of aryl halide
References and notes
(
1
3
1 mmol), [Rh(cod)Cl]
2
(0.05 mmol, 5 mol %), and Xantphos (0.1 mmol,
0 mol %) in 10 ml/mol formamide at room temperature and stirred for 2–
min. Then POCl (2 mmol) was added to the reaction mixture which was then
1
.
(a) Larock, R. C. Comprehensive Organic Transformation; VCH: New York, 1989;
b) Jia, X.; Yang, D.; Zhang, S.; Cheng, J. Org. Lett. 2009, 11, 4716–4719; (c) Jia, X.;
(
3
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heated in an oil bath at 135–140 °C for 24 h with continuous stirring under
nitrogen atmosphere. After 24 h the reaction mixture was cooled to room
2
3
.
.
temperature and poured into 40 ml saturated solution of NaHCO
was extracted into ethyl acetate (3 Â 15 ml). After drying over anhydrous
Na SO the combined ethyl acetate layer was concentrated by rotary
evaporation. All the prepared compounds were characterized by GC–MS
Shimadzu QP 2010).
3
. The product
2
4
,
4
.
(a) Rosenmund, K. W.; Struck, E. Ber. Dtsch. Chem. Ges. 1919, 2, 1749–1755; (b)
Lindley, J. Tetrahedron 1984, 40, 1433–1456.
(