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DOI: 10.1055/s-2005-872252
Palladium-Catalyzed Reaction of Bicyclic Hydrazines with Allyl- and Arylstannanes in Ionic Liquid [bmim]PF6: A Facile Method for the Synthesis of Substituted Hydrazinocyclopentene Derivatives
Publication History
Publication Date:
29 July 2005 (online)
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Abstract
A method for the synthesis of substituted hydrazinocyclopentenes by the palladium-catalyzed reaction of azabicyclic and tricyclic olefins with organostannanes is described. The reaction is facile with catalytic amount of Lewis acid and the rate of the reaction is enhanced by the use of ionic liquid, [bmim]PF6 as solvent.
Key words
bicyclic hydrazines - disubstituted cyclopentenes - ionic liquid [bmim]PF6 - allyltri-n-butyltin - Lewis acids - palladium catalyst
-
1a
Crimmins MT. Tetrahedron 1998, 54: 9229 -
1b
Berecibar A.Grandjean C.Siriwardena A. Chem. Rev. 1999, 99: 779 -
1c
Ogawa S.Morikawa T. Bioorg. Med. Chem. Lett. 2000, 10: 1047 - 2
Corey EJ.Narasaka K.Shibasaki M. J. Am. Chem. Soc. 1976, 98: 6417 -
3a
Kuang R.Ganguly AK.Chan T.-M.Pramanik BN.Blythin DJ.McPhail AT.Saksena AK. Tetrahedron Lett. 2000, 41: 9575 -
3b
Noble SA.Beddal NE.Beveridge AJ.Marr CLP.Mo CL.Penn CR.Storrer R.Woods JM. Nuleosides Nucleotides 1991, 10: 478 -
4a
Surman MD.Mulvihill MJ.Miller MJ. J. Org. Chem. 2002, 67: 4115 -
4b
Young RN. Eur. J. Med. Chem. 1999, 671 -
5a
Organometallics in Synthesis
Schlosser M. John Wiley and Sons; New York: 1994. Chap. 5. p.383-461 -
5b
Comprehensive Asymmetric Catalysis
Jacobsen EN.Pfaltz A.Yamamoto H. Springer; New York: 1999. Chap. 24. p.833-881 -
6a
Trost BM.Crawley ML. Chem. Rev. 2003, 103: 2921 -
6b
Trost BM. Chem. Pharm. Bull. 2002, 50: 1 -
7a
Surman MD.Miller MJ. Org. Lett. 2001, 3: 519 -
7b
Mulvihill MJ.Surman MD.Miller MJ. J. Org. Chem. 1998, 63: 4874 - 8
Yao M.-L.Adiwidjaja G.Kaufmann DE. Angew. Chem. Int. Ed. 2002, 41: 3375 - 9
Diels O.Bolm JH.Koll W. Justus Liebigs Ann. Chem. 1925, 443: 242 -
10a
Kosugi M.Kumura T.Oda H.Migita T. Bull. Chem. Soc. Jpn. 1993, 66: 3522 -
10b
Oda H.Ito K.Kosugi M.Migita T. Chem Lett. 1994, 1443 -
11a
Yadav JS.Reddy BVS.Sadasiv K.Satheesh G. Tetrahedron Lett. 2002, 43: 9695 -
11b
Wang S.-Y.Ji SJ.Loh TP. Synlett 2003, 2377 -
12a
Ionic Liquids in Synthesis
Wasserscheid P.Welton T. Wiley-VCH; Weinheim: 2002. -
12b
Leveque JM.Luche JL.Pefrier C.Roux R.Bonrath K. Green Chem. 2002, 357 - Recent reviews on ionic liquids:
-
13a
Dupont J.de Souza RF.Suarez PAZ. Chem. Rev. 2002, 102: 3667 -
13b
Zhao H.Malhotra SV. Aldrichimica Acta 2002, 35: 75 -
13c
Zhao D.Wu M.Kou Y.Min E. Catal. Today 2002, 74: 157 -
13d
Olivier-Bourbigou H.Magna L. J. Mol. Catal. A.: Chem. 2002, 182-183: 419 -
13e
Sheldon R. Chem. Commun. 2001, 2399 -
13f
Gordon CM. Appl. Catal. A 2001, 222: 101 -
13g
Earle MJ.Seddon KR. Pure Appl. Chem. 2000, 72: 1391 -
13h
Wasserscheid P.Keim W. Angew. Chem. Int. Ed. 2000, 39: 3773 -
13i
Welton T. Chem. Rev. 1999, 99: 2071 - 14
Gupta RC.Raynor CM.Stoodley RJ.Slawin AMZ.William DJ. J. Chem. Soc., Perkin Trans. 1 1988, 1773
References
Spectral Data for 4: R
f
= 0.35 (30% EtOAc-hexane). IR (neat): νmax = 3294, 3057, 2979, 2923, 1713, 1517, 1414, 1295, 1239, 1125, 1063, 909, 759, 713 cm-1. 1H NMR (300 MHz, CDCl3): δ = 6.52 (s, 1 H), 5.72-5.86 (m, 1 H), 5.59-5.63 (m, 2 H), 4.99-5.09 (m, 2 H), 4.55-4.57 (m, 1 H), 4.19 (q, 4 H), 2.85 (br s, 1 H), 2.31-2.53 (m, 3 H), 2.10-2.17 (m, 1 H), 1.27 (t, 6 H). 13C NMR (75 MHz, CDCl3): δ = 156.71, 155.94, 136.38, 132.82, 128.45, 116.25, 63.08, 62.35, 61.95, 47.62, 37.55, 35.17, 14.53, 14.46. LRMS (FAB): m/z calcd for C14H22N2O4 [M + 1]: 283.1658; found: 283.1666 [M + 1]. Anal. Calcd for C14H22N2O4: C, 59.56; H, 7.85; N, 9.92. Found: C, 59.86; H, 7.89; N, 10.18.
Data for 7: R
f
= 0.39 (60% EtOAc-hexane). IR (neat): νmax = 3433, 3175, 3067, 2954, 2923, 2851, 1769, 1697, 1604, 1506, 1429, 1249, 1130, 914, 770, 708 cm-1. 1H NMR (300 MHz, CDCl3): δ = 9.22 (br s, 1 H), 7.37-7.75 (m, 5 H), 5.73-5.75 (m, 1 H), 5.66-5.69 (m, 2 H), 5.02-5.11 (m, 2 H), 4.58-4.61 (m, 1 H), 2.89-2.90 (m, 1 H), 2.69-2.70 (m, 1 H), 2.48-2.49 (m, 1 H), 2.16-2.26 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 153.70, 151.65, 135.15, 132.72, 131.28, 128.84, 128.30, 127.90, 125.27, 117.05, 115.93, 59.75, 48.43, 37.62, 35.35. MS (LR-FAB): m/z calcd for C16H17N3O2 [M + 1]: 284.1399; found: 284.6529 [M + 1].
Data for 13: R
f
= 0.67 (25% EtOAc-hexane). IR (neat):
νmax = 3298, 2985, 2918, 1717, 1069, 914, 781 cm-1.
1H NMR (300 MHz, CDCl3): δ = 7.22-7.28 (m, 5 H), 6.68 (br s, 1 H), 5.85-5.87 (m, 1 H), 5.69-5.71 (m, 1 H), 4.73-4.76 (m, 1 H), 4.18-4.25 (q, 4 H), 4.01 (br s, 1 H), 2.61-2.67 (m, 2 H), 1.29 (t, 6 H). 13C NMR (75 MHz, CDCl3):
δ = 156.82, 156.21, 132.71, 129.71, 128.38, 127.47, 126.47, 67.32, 62.29, 62.06, 53.76, 35.15, 14.43, 14.19. MS (LR-FAB): m/z calcd for C17H22N2O4: 318.1580. Found: 318.6929.