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DOI: 10.1055/s-2007-984921
Silica-Immobilized CuI: An Efficient Reusable Catalyst for Three-Component Coupling Reaction of Aldehyde, Amine and Alkyne
Publication History
Publication Date:
24 July 2007 (online)
Abstract
Silica-supported copper catalysts were effectively used in the three-component coupling of aldehydes, amines and alkynes to afford the corresponding propargylamines in moderate to excellent yields. The catalyst was quantitatively recovered from the reaction by a simple filtration and reused for a number of cycles with almost consistent activity.
Key words
silica - copper - three-component coupling - propargylamines - reusable catalyst
-
1a
Armstrong RW.Combs AP.Tempst PA.Brown SD.Keating TA. Acc. Chem. Res. 1996, 29: 123 -
1b
Ugi I.Domling A.Werner B. J. Heterocycl. Chem. 2000, 37: 647 -
1c
Weber L.Illgen K.Almstetter M. Synlett 1999, 366 -
1d
Kamijo S.Yamamoto Y. J. Am. Chem. Soc. 2002, 124: 11940 -
1e
Domling A.Ugi I. Angew. Chem. Int. Ed. 2000, 39: 3169 -
1f
Cao C.Shi Y.Odom AL. J. Am. Chem. Soc. 2003, 125: 2880 -
1g
Zani L.Bolm C. Chem. Commun. 2006, 4263 - 2
Wei C.Zhang L.Li CJ. Synlett 2004, 1472 -
3a
Naota I.Takaya H.Murahashi SI. Chem. Rev. 1998, 98: 2599 -
3b
Dyker G. Angew. Chem. Int. Ed. 1999, 38: 1698 -
4a
Yan W.Wang R.Xu Z.Xu J.Lin L.Shen Z.Zhou Y. J. Mol. Catal. A: Chem. 2006, 255: 81 -
4b
Zhang Y.Santos AM.Herdtweck E.Mink J.Kuhn FE. New. J. Chem. 2005, 29: 366 -
4c
Wei C.Li Z.Li CJ. Org. Lett. 2003, 5: 4473 -
5a
Wei C.Li Z.Li CJ. Synlett 2004, 1472 -
5b
Wei C.Li CJ. J. Am. Chem. Soc. 2003, 125: 9584 - 6
Lo VKY.Liu Y.Wong MK.Che CM. Org. Lett. 2006, 8: 1529 -
7a
Shi L.Tu YQ.Wang M.Zhang FM.Fan CA. Org. Lett. 2004, 6: 1001 -
7b
Syeda HZS.Halder R.Karla SS.Das J.Iqbal J. Tetrahedron Lett. 2002, 43: 6485 -
7c
Kabalka GW.Wang L.Pagni RM. Synlett 2001, 676 - 8
Li CJ.Wei C. Chem. Commun. 2002, 268 - 9
Li Z.Wei C.Chen L.Varma RS.Li CJ. Tetrahedron Lett. 2004, 45: 2443 - 10
Park SB.Alper H. Chem. Commun. 2005, 1315 - 11
Choudary BM.Sridhar C.Kantam ML.Sreedhar B. Tetrahedron Lett. 2004, 45: 7319 - 12
Kantam ML.Prakash BV.Reddy CRV.Sreedhar B. Synlett 2005, 2329 - 13
Reddy KM.Babu NS.Prasad PSS.Lingaiah N. Tetrahedron Lett. 2006, 47: 7563 - 14
Kidwai M.Bansal V.Kumar A.Mozumdar S. Green Chem. 2007, in press -
15a
Mizuno N.Misono M. Chem. Rev. 1998, 98: 199 -
15b
Sartori G.Ballini R.Bigi F.Bosica G.Maggi R.Righi P. Chem. Rev. 2004, 104: 199 - 16
Corma A.Garcia H. Adv. Synth. Catal. 2006, 348: 1391 - 17
Likhar PR.Roy S.Roy M.Kantam ML.De R L. J. Mol. Catal. A: Chem. 2007, in press
References and Notes
Preparation of Imine-Modified Silica-Supported Copper Catalysts:17
SiO
2
-Py-Cu(OAc)
2
: SiO2-Py (1 g) was stirred with a solution of Cu(OAc)2 (1 mmol) in acetone (25 mL) for 24 h to get SiO2-Py-(CuOAc)2. The copper content was measured by ICP-AES and it was found to be 0.43 mmol/g. Similarly SiO2-Sal-Cu(OAc)2 (Cu: 0.41 mmol/g), SiO2-BPy-Cu(OAc)2 (Cu: 0.39 mmol/g), and SiO2-Thio-Cu(OAc)2 (Cu: 0.41 mmol/g) were prepared from Cu(OAc)2 in acetone. SiO2-Py-CuCl2 (Cu: 0.47 mmol/g) was prepared from an acetone solution of CuCl2. SiO2-Py-CuI was prepared from a MeCN solution of CuI and the copper content was 0.45 mmol/g.
Typical Procedure for A
³
Coupling Reaction: A mixture of aldehyde (1 mmol), amine (1.2 mmol), alkyne (1.5 mmol) and SiO2-Py-CuI (110 mg, 5 mol%) in MeCN (3 mL) was stirred in a round-bottomed flask at 90 °C under nitrogen. After completion of the reaction (monitored by TLC) the catalyst was filtered. After removing the solvent at reduced pressure, the crude material was purified by chromatography on silica gel using hexane-EtOAc mixture as eluent to afford the corresponding propargylamines. Spectroscopic data of the new compounds are given below:
Diallyl-[1-(4-bromophenyl)-3-phenylprop-2-ynyl]amine (Table 3, entry 12): 1H NMR (300 MHz, CDCl3): δ = 7.40-7.62 (m, 6 H), 7.28-7.38 (m, 3 H), 5.70-5.91 (m, 2 H), 5.24 (d, J = 17.0 Hz, 2 H), 5.12 (d, J = 9.3 Hz, 2 H), 4.99 (s, 1 H), 3.16-3.29 (m, 2 H), 2.90-3.06 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 138.5, 136.3, 131.8, 131.1, 129.8, 128.4, 122.8, 121.4, 117.4, 88.1, 84.7, 55.9, 53.5. ESI-MS: m/z = 368 [M + 1], 366 [M + 1], 271, 269, 146, 104. Anal. Calcd for C19H20BrN: C, 66.67; H, 5.89; N, 4.09. Found: C, 66.71; H, 5.92; N, 4.01.
4-[1-(4-Bromophenyl)-3-
p
-tolylprop-2-ynyl]morpholine (Table 3, entry 16): 1H NMR (300 MHz, CDCl3): δ = 7.45-7.61 (m, 4 H), 7.37 (d, J = 8.0 Hz, 2 H), 7.12 (d, J = 8.0 Hz, 2 H), 4.69 (s, 1 H), 3.61-3.79 (m, 4 H), 2.52-2.68 (m, 4 H), 2.38 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 138.5, 137.1, 131.8, 131.3, 130.3, 129.0, 121.7, 119.8, 89.1, 83.5, 67.2, 61.4, 49.8, 21.4. EI-MS: m/z = 371 [M+], 369 [M+], 285, 283, 214, 205, 189, 128, 86, 56. Anal. Calcd for C20H20BrNO: C, 64.87; H, 5.44; N, 3.78. Found: C, 64.89; H, 5.47; N, 3.75.