5322
Bandna et al. / Tetrahedron Letters 53 (2012) 5318–5322
Sperotto, E.; van Klink, G. P. M.; de Vries, J. G.; van Koten, G. J. Org. Chem. 2008,
73, 5625; (d) Sreedhar, B.; Arundhathi, R.; Reddy, P. L.; Kantam, M. L. J. Org.
Chem. 2009, 74, 7951; (e) Rout, L.; Sen, T. K.; Punniyamurthy, T. Angew. Chem.,
Int. Ed. 2007, 46, 5583; (f) Correa, A.; Carril, M.; Bolm, C. Angew. Chem., Int. Ed.
2008, 47, 2880; (g) Jammi, S.; Barua, P.; Rout, L.; Saha, P.; Punniyamurthy, T.
Tetrahedron Lett. 2008, 49, 1484; (h) Agawane, S. A.; Nagarkar, J. M. Tetrahedron
Lett. 2011, 52, 5220.
line participated in the same reaction with 2-chloronitrobenzene
and produced 28 in moderate yield (Table 4, entry 7). 2-Bromo
and 2-iodonitrobenzene also provided the corresponding products
25–26 (Table 4, entries 8–9).
Evaluation of recyclability was done on the test substrate, 4-
chloronitrobenzene. After completion of C–O cross coupling reac-
tion of phenol with 4-chloronitrobenzene, the reaction mixture
was treated with water and extracted with ethyl acetate. The
recovered catalyst was washed with acetone, dried, and reused
for further reaction. The catalytic activity of SS-Pd remained almost
the same up to seven runs as indicated by the yields of the corre-
sponding product (Table 5).
2. (a) Evano, G.; Blanchard, N.; Toumi, M. Chem. Rev. 2008, 108, 3054; (b) Corbet,
J.-P.; Mignani, G. Chem. Rev. 2006, 106, 2651; (c) Buchwald, S. L.; Mauger, C.;
Mignani, G.; Scholz, U. Adv. Synth. Catal. 2006, 348, 23; (d) Surry, D. S.;
Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47, 6338.
3. Trump, R. P.; Blanc, J.-B. E.; Stewart, E. L.; Brown, P. J.; Caivano, M.; Gray, D. W.;
Hoekstra, W. J.; Wilson, T. M.; Han, B.; Turnbull, P. J. Comb. Chem. 2007, 9, 107;
(b) Tufano, M.D. U.S. Patent 4287372.
4. (a) Junge, K.; Wendt, B.; Shaikh, N.; Beller, M. Chem. Commun. 2010, 46, 1769;
(b) Buchanan, R.A.; Stultus, J.S. U.S. Patent 5117002.
Amino substituted cross coupled products are essential for de-
sign based synthesis of bioactive molecules and amines are not
suitable substrates for cross coupling reactions due to requirement
of harsh reaction conditions. Therefore a sequential process is
desirable for both cross coupling as well as reduction of nitro group
to afford desired amino substituted cross coupled product by using
the same catalyst. To demonstrate the feasibility of this approach, a
one-pot sequential synthesis was attempted. 4-Chloronitroben-
zene was coupled with phenol as well as cresol to give 1-(4-nitro-
phenoxy)benzene and 1-(4-nitrophenoxy)-4-methylbenzene. The
completion of reaction was monitored by TLC and then the reac-
tion mixture treated with Et3SiH and continued for another
30 min to 1 h. Finally the amino substituted cross coupled products
29 and 30 were isolated in good yields (Scheme 1). Similar sequen-
tial reaction was also performed including C–N cross coupling of 2-
chloronitrobenzene with pyrrolidine followed by reduction of nitro
group afforded 31 (Scheme 2).
In conclusion, an efficient method is described for the cross cou-
pling of oxygen, sulfur, and nitrogen nucleophiles with nitro
substituted aryl halides using SS-Pd under ligand-free and milder
basic conditions. A variety of substrates undergo the cross coupling
reaction in high yield. In addition, a one-pot sequential cross cou-
pling and nitro reduction is achieved. The catalyst can be recycled
up to seven runs without significant loss of activity.
5. (a) Gangjee, A.; Zeng, Y.; Talreja, T.; McGuire, J. J.; Kisliuk, R. L.; Queener, S. F. J.
Med. Chem. 2007, 50, 3046; (b) Jarkas, N.; McConathy, J.; Voll, R. J.; Goodman,
M. M. J. Med. Chem. 2005, 48, 4254.
6. (a) Urgaonkar, S.; Xu, J. H.; Verkade, J. G. J. Org. Chem. 2003, 68, 8416; (b) Reddy,
C. V.; Kingston, J. V.; Verkade, J. G. J. Org. Chem. 2008, 73, 3047.
7. (a) Surry, D. S.; Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47, 6338; (b)
Yamamoto, T.; Nishiyama, M.; Koie, Y. Tetrahrdron Lett. 1998, 39, 2367; (c)
Tewari, A.; Hein, M.; Zapf, A.; Beller, M. Tetrahedron 2005, 61, 9705; (d) Hill, L.
L.; Moore, L. R.; Huang, R. C.; Craciun, R.; Vincent, A. J.; Dixon, D. A.; Chou, J.;
Woltermann, C. J.; Shaughnessy, K. H. J. Org. Chem. 2006, 71, 5117.
8. (a) Marion, N.; Navarro, O.; Mei, J. G.; Stevens, E. D.; Scott, N. M.; Nolan, S. P. J.
Am. Chem. Soc. 2006, 128, 4101; (b) Navarro, O.; Marion, N.; Mei, J. G.; Nolan, S.
P. Chem. Eur. J. 2006, 12, 5142; (c) Organ, M. G.; Abdel-Hadi, M.; Avola, S.;
Dubovyk, I.; Hadei, N.; Kantchev, E. A. B.; Brien, C. J. O.; Sayah, M.; Valente, C.
Chem. Eur. J. 2008, 14, 2443.
9. (a) Hartwig, J. F. Acc. Chem. Res. 2008, 41, 1534; (b) Shen, Q.; Ogata, T.; Hartwig,
J. F. J. Am. Chem. Soc. 2008, 130, 6586.
10. (a) Reddy, C. V.; Kingston, J. V.; Verkade, J. G. J. Org. Chem. 2008, 73, 3047; (b)
Xie, X.; Zhang, T. Y.; Zhang, Z. J. Org. Chem. 2006, 71, 6522; (c) Singer, R. A.;
Dore, M. L.; Sieser, J. E.; Berliner, M. A. Tetrahedron Lett. 2006, 47, 3727; (d)
Ackermann, L.; Born, R. Angew. Chem., Int. Ed. 2005, 44, 2444; (e) Ackermann, L.;
Spatz, J. H.; Gschrei, C. J.; Born, R.; Althammer, A. Angew. Chem., Int. Ed. 2006,
45, 7627; (f) Dai, Q.; Gao, W. Z.; Liu, D.; Kapes, L. M.; Zhang, X. M. J. Org. Chem.
2006, 71, 3928; (g) So, C. M.; Zhou, Z.; Lau, C. P.; Kwong, Y. F. Angew. Chem., Int.
Ed. 2008, 47, 6402.
11. (a) Harkal, S.; Kumar, K.; Michalik, D.; Zapf, A.; Jackstell, R.; Rataboul, F.;
Riermeier, T.; Monsees, A.; Bellera, M. Tetrahedron Lett. 2005, 46, 3237; (b)
Parrish, C. A.; Buchwald, S. L. J. Org. Chem. 2001, 66, 2498; (c) Torraca, K. E.;
Huang, X.; Parrish, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 2001, 123, 10770; (d)
Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999,
121, 3224; (e) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem.
2002, 67, 5553.
12. Mo, J.; Eom, D.; Kim, S. H.; Lee, P. H. Chem. Lett. 2011, 40, 980.
13. Murata, M.; Buchwald, S. L. Tetrahedron 2004, 60, 7397.
Acknowledgments
14. (a) Fernandez-Rodriguez, M. A.; Shen, Q. L.; Hartwig, J. F. Chem. Eur. J. 2006, 12,
7782; (b) Fernandez-Rodriguez, M. A.; Shen, Q. L.; Hartwig, J. F. J. Am. Chem. Soc.
2006, 128, 2180.
15. (a) Kogan, V.; Aizenshtat, Z.; Popovitz-Biro, R.; Neumann, R. Org. Lett. 2002, 4,
3529; (b) Jiang, Z.; She, J.; Lin, X. Adv. Synth. Catal. 2009, 351, 2558; (c)
Velmathi, S.; Vijayaraghavan, R.; Amarendar, Ch.; Pal, R. P.; Vinu, A. Synlett
2010, 2733.
Authors are grateful to Dr. P.S. Ahuja, Director IHBT for provid-
ing necessary facilities during the course of the work. We gratefully
acknowledge the financial assistance from the Department of Sci-
ence & Technology (Nano Mission), New Delhi (Grant No. SR/NM/
NS-95/2009). Bandna (SRF), NRG (JRF), and AKS (SRF), and DS
(SRF) thank the CSIR and the UGC, New Delhi for awarding the
fellowships.
16. (a) Das, P.; Sharma, D.; Shil, A. K.; Kumari, A. Tetrahedron Lett. 2011, 52, 1176;
(b) Bandna; Aggarwal, N.; Das, P. Tetrahedron Lett. 2011, 52, 4954; (c) Shil, A. K.;
Sharma, D.; Guha, N. R.; Das, P. Tetrahedron Lett. 2012, 53, 4858–4861.
17. (a) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67,
5553; (b) Urgaonkar, S.; John, G.; Verkade, J. G. J. Org. Chem. 2004, 69, 9135.
18. 1-(4-Nitrophenoxy)benzene (1): A mixture of 4-nitrochlorobenzene (100 mg,
0.63 mmol), phenol (70.58 mg, 0.75 mmol), SS-Pd (284.5 mg, 0.01 mmol of Pd),
and K2CO3 (174.14 mg, 1.26 mmol) in DMF (2 ml) was placed in a round
bottom flask. The reaction mixture was then heated at 80 °C under magnetic
stirring for 6 h. The completion of reaction was monitored by TLC. After cooling
to room temperature, the mixture was diluted with water, and extracted with
ethyl acetate three times (3 Â 10 ml). The combined organic layer was
concentrated to yield the crude product, which was purified by column
chromatography on silica gel (hexane/EtOAc :: 99:1) to yield 1-(4-
Nitrophenoxy)benzene 1 as a yellow solid (115 mg, 84%), mp 57–58 °C; 1H
NMR (300 MHz, CDCl3-d1) d 8.17–8.21 (m, 2H), 7.42–7.47 (m, 2H), 7.12 (m,1H),
7.06–7.09 (m, 2H), 7.0–7.04 (m, 2H) ; 13C NMR (75 MHz, CDCl3-d1) d 163.75,
155.14, 143.06, 130.35 (2C), 126.30 (2C), 125.81, 120.92 (2C), 117.50 (2C).
Supplementary data
Supplementary data (general experimental procedures and
characterization data for all compounds) associated with this arti-
References and notes
1. (a) Louie, J.; Hartwig, J. F. Tetrahedron Lett. 1995, 36, 3609; (b) Shelby, Q.;
Kataoka, N.; Mann, G.; Hartwig, J. F. J. Am. Chem. Soc. 2000, 122, 10718; (c)