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

K. V. Radhakrishnan; V. S. Sajisha; S. Anas; K. Syam Krishnan

doi:10.1055/s-2005-872252

LETTER

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

K. V. Radhakrishnan*, V. S. Sajisha, S. Anas, K. Syam Krishnan
Organic Chemistry Section, Chemical Sciences Division, Regional Research Laboratory (CSIR), Trivandrum-695 019, Kerala, India
Fax: +91(471)2491712, +91(471)2490186; e-Mail: radhupreethi@rediffmail.com;

Abstract

All articles of this category

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

Full Text

References

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

15

Spectral Data for 4: R _f = 0.35 (30% EtOAc-hexane). IR (neat): ν_max = 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): ν_max = 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):
ν_max = 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.