Z.S. Qureshi et al. / Catalysis Today 198 (2012) 148–153
153
78–89% yields of amide products (entries 7–9). Encouraged
References
with these results, the PS-Pd-NHC complex was then subjected
for aminocarbonylation reaction of heterocyclic primary amines
such as 2-aminopyridine, 3-aminopyridine, 3-aminoquinoline with
iodobenezene affording moderate to good yield of desired amides
(entries 10–12). It was noticed that bicyclic heteroaryl iodide such
reaction with aniline, providing 75% yield of expected amide (entry
13).
[1] (a) D. Valenline Jr., J.W. Tilley, R.A. LeMahieu, The Journal of Organic Chemistry
46 (1981) 4614;
(b) L. Classar, M. Foa, A. Gardano, Journal of Organometallic Chemistry 121
(1976) 55;
(c) V.V. Grushin, H.J. Alper, Journal of Chemical Society, Chemical Communica-
tions (1992) 611;
(d) I.P. Beletskaya, A.L. Lapidas, K.B. Petrovskii, Russian Journal of Organic
Chemistry 34 (1998) 1464;
(e) Y.S. Lin, A. Yamamoto, Journal of Organometallic Chemistry 645 (2002)
152.
Moreover, the generality of our catalytic system (PS-Pd-NHC)
under the present reaction conditions was further explored for the
aminocarbonylation of secondary amines (Table 3). The aminocar-
bonylation of iodobenzene with N-methyl aniline provided the
corresponding N-methyl-N-phenyl-benzamide product in good
yield (entry 1). The aminocarbonylation coupling reaction of 4-
iodotoluene and 4-acetyl iodobenzene with N-methyl aniline using
PS-Pd-NHC complex as a catalyst provides 88% and 81% yield,
respectively, of the desired products (entries 2–3). Unfortunately,
aromatic secondary amine, i.e. biphenyl amine was not compat-
ible with this aminocarbonylation coupling reaction (entry 4).
The aminocarbonylation of iodobenzene with aliphatic secondary
amines such as diethyl amine and dibutyl amine was also found
to provide excellent yields of amide products (entries 5–6). The
present catalytic system also worked very well for the aminocar-
bonylation reaction of iodobenzene with aliphatic cyclic secondary
amines (pyrrolidine and morpholine) providing 91% and 79% yield,
respectively (entries 7–8).
[2] (a) A. Schoenberg, R.F. Heck, Journal of Organometallic Chemistry 39 (1974)
3327;
(b) R.J. Perry, B.D. Wilson, Organometallics 13 (1994) 3346;
(c) T. Takahashi, H. Inoue, S. Tomida, T. Doi, A.M. Bray, Tetrahedron Letters 40
(1999) 7843;
(d) W. Magerlei, A.F. Indolesi, M. Beller, Journal of Organometallic Chemistry
641 (2002) 30.
[3] (a) A. Schoenberg, I. Barrolatti, R.F. Heck, Journal of Organometallic Chemistry
39 (1974) 3318;
(b) Y. Ben-David, M. Portnoy, D. Milstein, Journal of the American Chemical
Society 111 (1989) 8742;
(c) J. Yang, A. Haynes, P.M. Maitlis, Chemical Communications (1999) 179;
(d) V. Calo, P. Giannoccaro, A. Nacci, A. Monopoli, Tetrahedron Letters 42 (2001)
3299;
(e) W. Magerlein, M. Beller, A.F. Indolese, Journal of Molecular Catalysis A:
Chemical 156 (2000) 213.
[4] (a) Y. Ben-David, M. Portnoy, D. Milstein, Journal of the American Chemical
Society (Commununication) (1989) 1816;
(b) T. Okano, N. Harada, J. Kiji, Bulletin of the Chemical Society of Japan 67
(1994) 2329.
[5] J.K. Stille, Pure Applied Chemistry 57 (1985) 1771.
[6] (a) H.M. Colquhoun, D.H. Thompson, M.V. Twigg, Carbolylation Direct Synthesis
of Carbonyl Compounds, Plenum Press, New York, 1991;
(b) J. Tsuji, Palladium Reagents and Catalysis, Wiley, Chichester, 1995;
(c) R.F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, New
York, 1985.
[7] A. Schoenberg, R.F. Heck, Journal of Organic Chemistry 39 (1974) 3327.
[8] M. Cai, Y. Huang, R. Hu, C. Song, Journal of Molecular Catalysis A: Chemical 212
(2004) 151.
[9] M. Cai, H. Zhao, Y. Huang, Journal of Molecular Catalysis A: Chemical 238 (2005)
41.
[10] R. Skoda-Foldes, E. Takacs, J. Horvath, Z. Tuba, L. Kollar, Green Chemistry 5
(2003) 643.
Thus the developed protocol is found to be general for the
aminocarbonylation coupling reaction of various structurally and
electronically different aryl iodides with aliphatic/aromatic pri-
mary and secondary amines providing good to excellent yield of
the desired amides, illustrates broad application of the developed
methodology and its remarkable functional group compatibility on
both reagent was observed.
[11] (a) W. Herrmann, Angewandte Chemie, International Edition 41 (2002) 1290;
(b) K. Ofele, Journal of Organometallic Chemistry 12 (1968) 42;
(c) H. Wanzlick, H. Schonherr, Angewandte Chemie, International Edition 80
(1968) 154.
[12] (a) J.W. Sprengers, J. Wassenaar, N.D. Clement, K.J. Cavell, C.J. Elsevier, Ange-
wandte Chemie, International Edition 44 (2005) 2026;
(b) P. Hauwert, R. Boerleider, S. Warsink, J.J. Weigand, C.J. Elsevier, Journal of
American Chemical Society 132 (2010) 16900.
[13] (a) Z.S. Qureshi, K.M. Deshmukh, P.J. Tambade, B.M. Bhanage, Synthesis (2011)
243;
(b) J. Byun, Y. Lee, Tetrahedron Letters 45 (2004) 1837;
(c) J. Kim, B. Jun, J. Byun, Y. Lee, Tetrahedron Letters 45 (2004) 5827.
[14] (a) M.V. Khedkar, S.R. Khan, D.N. Sawant, D.B. Bagal, B.M. Bhanage, Advanced
Synthesis & Catalysis 353 (2011) 3415;
4. Conclusion
In conclusion, an efficient, phosphine-free protocol for the
aminocarbonylation reaction of aryl iodides with primary and sec-
ondary amines in aqueous medium using PS-Pd-NHC complex as
a heterogeneous and recyclable catalyst has been developed. The
reaction was optimized with respect to various parameters and
enabled aminocarbonylation reaction of different aryl iodides with
variety of primary and secondary amines affording good to excel-
lent yield of desired products thus illustrating broad application of
the methodology. The catalyst can be easily recycled by simple fil-
tration process up to four consecutive recycle without loss in any
activity and selectivity. The developed protocol with use of water
as a solvent and recyclable catalytic system introduces a success
toward green approach in organic synthesis.
(b) M.V. Khedkar, P.J. Tambade, Z.S. Qureshi, B.M. Bhanage, European Journal
of Organic Chemistry 6981 (2010);
(c) P.J. Tambade, Y.P. Patil, B.M. Bhanage, Applied Organometallic Chemistry 23
(2009) 235;
(d) P.J. Tambade, Y.P. Patil, M.J. Bhanushali, B.M. Bhanage, Synthesis 2347
(2008);
(e) P.J. Tambade, Y.P. Patil, M.J. Bhanushali, B.M. Bhanage, Tetrahedron Letters
49 (2008) 2221;
Acknowledgement
(f) P.J. Tambade, Y.P. Patil, A.G. Panda, B.M. Bhanage, European Journal of
Organic Chemistry (2009) 3022.
[15] D.B. Bagal, Z.S. Qureshi, K.P. Dhake, S.R. Khan, B.M. Bhanage, Green Chemistry
13 (2011) 1490.
The financial assistance from Indira Gandhi Centre for Atomic
Research (IGCAR) Kalpakkam, India is kindly acknowledged.