Subscribe to RSS
DOI: 10.1055/s-2004-815420
Cu(acac)2 Immobilized in Ionic Liquids: A Novel and Recyclable Catalytic System for Aziridination of Olefins Using PhI=NTs as Nitrene Donor
Publication History
Publication Date:
12 January 2004 (online)
![](https://www.thieme-connect.de/media/synlett/200403/lookinside/thumbnails/10.1055-s-2004-815420-1.jpg)
Abstract
Copper(II) acetylacetonate immobilized in ionic liquids efficiently catalyzes aziridination of olefins in good yields at a faster rate than the earlier reported methods using PhI=NTs as a nitrene donor with easy catalyst/solvent recycling.
Key words
copper acetylacetonate - ionic liquids - aziridination - olefins - PhI=NTs
-
1a
Kump JEG. Comprehensive Organic Synthesis Vol. 7:Trost BM.Fleming I. Pergamon; Oxford: 1991. p.4691 -
1b
Pearson WH.Lian BW.Bergmeier SC. In Comprehensive Heterocyclic Chemistry II Vol. IA:Padwa A. Pergamon Press; New York: 1996. p.1 -
2a
Aires-de-Sousa J.Prabhakar S.Lobo AM.Rosa AM.Gomes MJS.Corvo MC.Williams DJ.White AJP. Tetrahedron: Asymmetry 2001, 12: 3349 -
2b
Chenna PHD.Dauban P.Ghini A.Baggio R.Garland MT.Burton G.Dodd RH. Tetrahedron 2003, 59: 1009 - 3
McCoull W.Davis FA. Synthesis 2000, 1347 -
4a
Atkinson RS. Tetrahedron 1999, 55: 1519 -
4b
Hancock MT.Pinhas AR. Tetrahedron Lett. 2003, 44: 5457 - 5
Sweeney JB. Chem. Soc. Rev. 2002, 31: 247 -
6a
Evans DA.Faul MM.Bilodeau MT.Anderson BA.Barnes DM. J. Am. Chem. Soc. 1993, 115: 5328 -
6b
Li Z.Conser KR.Jacobsen EN. J. Am. Chem. Soc. 1993, 115: 5326 -
6c
Evans DA.Faul MM.Bilodeau MT. J. Am. Chem. Soc. 1994, 116: 2742 -
7a
Jeong JU.Tao B.Sagasser I.Henniges H.Sharpless KB. J. Am. Chem. Soc. 1998, 120: 67 -
7b
Antunes AMM.Marto SJL.Branco PS.Prabhakar S.Lobo AM. Chem. Commun. 2001, 405 -
7c
Ando T.Minakata S.Ryu I.Komatsu M. Tetrahedron Lett. 1998, 39: 309 -
7d
Vyas R.Chanda BM.Bedekar AV. Tetrahedron Lett. 1998, 39: 4715 -
7e
Vyas R.Chanda BM.Belhekar AA.Patel DR.Ram RN.Bedekar AV. J. Mol. Catal. A: Chem. 2000, 160: 237 -
7f
Chanda BM.Belhekar AA.Bedekar AV. J. Org. Chem. 2001, 66: 30 - 8
Hansen KB.Finney NS.Jacobsen EN. Angew. Chem., Int. Ed. Engl. 1995, 34: 676 - 9
Casarrubios L.Perez JA.Brookhart M.Templeton JL. J. Org. Chem. 1996, 61: 8358 - 10
Sengupta S.Mondal S. Tetrahedron Lett. 2000, 41: 6245 - 11
Xie WH.Fang JW.Li JI.Wang PG. Tetrahedron 1999, 55: 12929 -
12a
Langham C.Piaggo P.Bethell D.Lee DF.McMorn P.Bulman Page PC.Willock DJ.Sly C.Hancock FE.King F.Hutchings GJ. Chem. Commun. 1998, 1601 -
12b
Langham C.Taylor S.Bethell D.McMorn P.Bulman Page PC.Willock DJ.Sly C.Hancock FE.King F.Hutchings GJ. J. Chem. Soc., Perkin Trans. 2 1999, 1043 - 13
Jun-Long Z.Chi-Ming C. Org. Lett. 2002, 4: 1911 - 14
Mar Diaz-requejo M.Perez PJ. J. Organomet. Chem. 2001, 617-618: 110 -
15a
Welton T. Chem Rev. 1999, 99: 2071 -
15b
Seddon KR. Kinetics and Catalysis 1996, 37: 693 -
15c
Hussey CL. Pure Appl. Chem. 1988, 60: 1763 -
15d
Larsen AS.Holbrey JD.Tham FS.Reed CA. J. Am. Chem. Soc. 2000, 122: 7264 - For recent reviews, see:
-
16a
Seddon KR. J. Chem. Tech. Biotechnol. 1997, 68: 351 -
16b
Holbrey J.Seddon KR. Clean Prod. Proc. 1999, 1: 223 -
16c
Earle MJ.Seddon KR. Pure Appl. Chem. 2000, 72: 1391 -
16d
Wasserscheid P.Keim W. Angew. Chem. Int. Ed. 2000, 39: 3772 -
17a
Chauvin Y.Mubmann L.Olivier H. Angew. Chem., Int. Ed. Engl. 1995, 34: 2698 -
17b
Monteiro A.Zinn FK.de souza RF.Dupont J. Tetrahedron: Asymmetry 1997, 8: 177 -
17c
Song CE.Shim WH.Roh EJ.Lee S.Choi JH. Chem. Commun. 2001, 1122 -
17d
Xu L.Chen W.Xiao J. Organometallics 2000, 19: 1123 -
18a
Song CE.Shim WH.Roh EJ.Lee S.Choi JH. Chem. Commun. 2001, 1695 -
18b
Fraile JM.Garcia JI.Herrerias CI.Mayoral JA.Carrie D.Vaultier M. Tetrahedron: Asymmetry 2001, 12: 1891 -
18c
Rosa JN.Afonso CAM.Santos AG. Tetrahedron 2001, 57: 4189 -
19a
Song CE.Roh E. Chem. Commun. 2000, 837 -
19b
Song CE.Oh CR.Roh EJ.Choo D. Chem. Commun. 2000, 1743 -
19c
Chen SL.Ji SJ.Loh TP. Tetrahedron Lett. 2003, 44: 2405 - 20
Sun W.Xia CG.Wang HW. Tetrahedron Lett. 2003, 44: 2409 -
21a
Suaarez PAZ.Dullius JEL.Einloft S.de souza RF.Dupont J. Polyhedron 1996, 15: 1217 -
21b
Park S.Kazlauskas RJ. J. Org. Chem. 2001, 66: 8395
References
Typical Experimental Procedure: Cu(acac)2 (0.010 g, 7.7 mol%), styrene (0.56 ml, 5 mmol) and PhI=NTs (0.372 g, 1 mmol) were added to the ionic liquid (1 mL) and the reaction mixture was stirred at r.t. for 25 min. The reaction was monitored by the disappearance of PhI=NTs. After completion of the reaction, the product was extracted with Et2O (3 × 4 mL) by simple decantation and purified by column chromatography on silica gel with petroleum ether and EtOAc (95:5) as eluent. The ionic liquid containing Cu(acac)2 was dried under vacuum for the next run. The resulting products were analyzed by NMR. Yield: 0.240 g, 88%. 1H NMR (400 MHz, CDCl3): δ = 7.86 (d, J = 8.3 Hz, 2 H, Ar-H), 7.27 (m, 7 H, Ar-H), 3.77 (dd, J
cis
= 7.2 Hz,
J
trans
= 4.5 Hz, 1 H, CHPh), 2.98 (d, J = 7.8 Hz, 1 H, cis-CH-aziridine) 2.43 (s, 3 H, Ar-Me), 2.38 (d, J = 4.4 Hz, 1 H, trans-CH-aziridine).