2-Methyl-1,3-Cyclopentane and -Cyclohexanediones: Nucleophiles and Leaving Groups in Palladium-Catalyzed Allylations

Synlett

Volumn 1996, Issue 9, 1996, Pages 850-852

  Vicart, Nicolas ^a   Goré, Jacques ^a   Cazes, Bernard ^a  

^a UNIVERSITÉ LYON 1   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0010443390     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1996-5591     Document Type: Article

References (32)

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2. (a) Phenoxy as leaving group: see Ref 1 and "interalia" Brakta, M.; Lhoste, P.; Sinou, D. J. Org. Chem. 1989, 54, 1890.
3. (b) Phenoxy as nucleophile, see: Goux, C.; Lhoste, P.; Sinou, D. Synlett 1992, 725.
4. (a) Amines as nucleophiles, see : Ref. 1, p 329-334 and Besson, L.; Goré, J.; Cazes, B. Tetrahedron Lett. 1995, 36, 3857.
5. (b) Palladium-catalyzed reactions of allylic amines : for leading references, see Bourgeois-Cury, A., Doan, D.; Goré, J. Tetrahedron Lett. 1992, 33, 1277.
6. (a) Use of sulfinates as nucleophiles: Hiroi, K.; Makino, K.; Chem. Lett. 1996, 617. Inomata, K.; Yamamoto, T.; Kotake, H. Chem. Lett. 1981, 1357. Trost, B.M.; Organ, M.G.; O'Doherty, A. J. Am. Chem. Soc. 1995, 117, 9662. Eichelmann, H.; Gais, H.J. Tetrahedron Asymmetry 1995, 6, 643.
7. (a) Use of sulfinates as nucleophiles: Hiroi, K.; Makino, K.; Chem. Lett. 1996, 617. Inomata, K.; Yamamoto, T.; Kotake, H. Chem. Lett. 1981, 1357. Trost, B.M.; Organ, M.G.; O'Doherty, A. J. Am. Chem. Soc. 1995, 117, 9662. Eichelmann, H.; Gais, H.J. Tetrahedron Asymmetry 1995, 6, 643.
8. (a) Use of sulfinates as nucleophiles: Hiroi, K.; Makino, K.; Chem. Lett. 1996, 617. Inomata, K.; Yamamoto, T.; Kotake, H. Chem. Lett. 1981, 1357. Trost, B.M.; Organ, M.G.; O'Doherty, A. J. Am. Chem. Soc. 1995, 117, 9662. Eichelmann, H.; Gais, H.J. Tetrahedron Asymmetry 1995, 6, 643.
9. (a) Use of sulfinates as nucleophiles: Hiroi, K.; Makino, K.; Chem. Lett. 1996, 617. Inomata, K.; Yamamoto, T.; Kotake, H. Chem. Lett. 1981, 1357. Trost, B.M.; Organ, M.G.; O'Doherty, A. J. Am. Chem. Soc. 1995, 117, 9662. Eichelmann, H.; Gais, H.J. Tetrahedron Asymmetry 1995, 6, 643.
10. (b) Sulfinates as leaving group: Trost, B.M.; Schmuff, N.R.; Miller, M.J. J. Am. Chem. Soc. 1980, 120, 5979.
11. (c) Palladium-catalyzed isomerisation of allylic sulfones: Monteiro, N.; Balme, G.; Goré, J. Synlett, 1992, 227 and references therein.
12. (a) Chiusoli, G.P.; Costa, M.; Pallini, L.; Terrenghi, G.Transition Met. Chem. 1981, 6, 317 and 1982, 7, 304.
13. (a) Chiusoli, G.P.; Costa, M.; Pallini, L.; Terrenghi, G.Transition Met. Chem. 1981, 6, 317 and 1982, 7, 304.
14. (b) Burgess, K. Tetrahedron Lett. 1985, 26, 3049 and J. Org. Chem. 1987, 52, 2046.
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16. (c) Shimidzu, I.; Ohashi, Y.; Tsuji, J. Chem. Lett. 1987, 1157.
17. (d) Bäckvall, J.E.; Vagberg, J.O.; Zercher, C.; Genêt, J.P.; Denis, A. J. Org. Chem. 1987, 52, 5430.
18. (a) Andersson, P.G.; Bäckvall J.E. J. Org. Chem. 1991, 56, 5349.
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20. (c) for a discussion, see Trost, B.M.; Bunt, R.C. Tetrahedron Lett., 1993, 34, 7513.
21. (a) Vicart, N.; Cazes, B.; Goré, J. Tetrahedron Lett. 1995, 36, 535.
22. (b) Vicart, N.; PhD Thesis, Université Claude Bernard, Lyon, 1995.
23. (a) Chaptal, N.; Colovray-Gotteland, V.; Grandjean, C.; Cazes, B.; Goré, J.Tetrahedron Lett. 1991, 32, 1795.
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25. 13C NMR spectroscopies and mass spectral determinations.
26. For the pKa values of 1,3-cycloalkanediones in DMSO, see: (a) Bordwell, F.G. Acc. Chem. Res. 1988, 21, 456. (b) Arnett, E.M.; Maroldo, S.G.; Schilling, S.L.; Harrelson, J.A. J. Am. Chem. Soc. 1984, 106, 6759. 2-methyl-1,3-cyclopentanedione 4a (pKa = 10.42); 2-methyl-1,3-cyclohexanedione 6a (pKa ∼ 11; pKa = 11.3 for methyldimedone); compare with AcOH (pKa = 12.3), acetoxy group being the more common leaving group in this type of reaction (see Ref. 1).
27. For the pKa values of 1,3-cycloalkanediones in DMSO, see: (a) Bordwell, F.G. Acc. Chem. Res. 1988, 21, 456. (b) Arnett, E.M.; Maroldo, S.G.; Schilling, S.L.; Harrelson, J.A. J. Am. Chem. Soc. 1984, 106, 6759. 2-methyl-1,3-cyclopentanedione 4a (pKa = 10.42); 2-methyl-1,3-cyclohexanedione 6a (pKa ∼ 11; pKa = 11.3 for methyldimedone); compare with AcOH (pKa = 12.3), acetoxy group being the more common leaving group in this type of reaction (see Ref. 1).
28. -2 mm Hg) and condensation at -78°C.
29. Vo Quang, Y.; Marais, D.; Vo Quang, L.; Le Goffic, F. Tetrahedron Lett. 1983, 24, 5209.
30. 5: C, 59.00; H, 8.25. Found : C, 59.36; H, 8.56.
31. Billups, W.E.; Erkes, R.S.; Reed, L.E. Syn. Commun. 1980, 10, 147.
32. Chatterjee, S.; Negishi, E.I. J. Org. Chem. 1985, 50, 3406.