Palladium(0)-Catalyzed Reaction of. α,β-Epoxy Ketones Leading to β-Diketones

Journal of the American Chemical Society

Volumn 102, Issue 6, 1980, Pages 2095-2096

  Suzuki, M ^a   Watanabe, A ^a   Noyori, R ^a  

^a NAGOYA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000780620     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00526a059     Document Type: Letter

References (14)

1. Hauser, C. R.; Swamer, F. W.; Adams, J. T. Org. React. 1954, 8, 59.
2. Schick, H.; Lehmann, G.; Hilgetag, G. Angew. Chem., Int. Ed. Engl. 1967, 6, 80.
3. Granda, V. J.; Lindberg, G. W.; Wendler, N. L.; Pines, S. H. J. Org. Chem. 1967, 32, 1236.
4. Newkome, G. R.; Roach, L. C.; Montelaro, R. C.; Hill, R. K. J. Org. Chem. 1972, 37, 2098. Other conventional methods follow: (e) Schank, K.; Eistert, B. Chem. Ber. 1966, 99, 1414.
5. Ito, Y.; Fujii, S.; Saegusa, T. J. Org. Chem. 1976, 41, 2073. a,βEpoxy ketones are accessible under neutral conditions by epoxidation of allylic alcohols followed by oxidation of the hydroxyl group: Sharpless, K. B.; Michaelson, R. C. J. Am. Chem. Soc. 1973, 95, 6136. Pfitzner, K. E.; Moffatt, J. G. J. Org. Chem. 1965, 87, 5661. For the synthesis from a,βunsaturated ketones by basic hydrogen peroxide oxidation, see Lewis, S. N. “Oxidation”, Augustine, R. L., Ed.; Marcel Dekker: New York, 1969; Vol. 1, Chapter 5.
6. Coulson, D. R. Inorg. Syn. 1972, 13, 121. The complex should be purified before use by recrystallization from a 3:1 THF-ether mixture at 0 °C.
7. The ligand effect was examined in detail in the reaction of 3,4-epoxy-2-pentanone. Other multidentate phosphine ligands, such as bis(diphenyl-phosphino)propane, (+)-2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(di-phenylphosphino)butane (diop), or bis(2-diphenylphosphlnoethyl)phenyl-phosphine (a tridentate ligand), worked much less effectively. In the presence of such ligands, metal precipitation was avoided, but consumption of the starting material was slow. Unidentate ligands, P(CeH5)3, P(CeH5)2CH3, P(CH3)2C6H5, P(n-C4H9)3, etc., did not give any satisfactory results either. See also entries 1, 6, 9, and 10 in Table I.
8. Lick, C.; Schank, K. Chem. Ber. 1978, 111, 2461, and references cited therein.
9. Trost, B. M. Tetrahedron, 1977, 33, 2615.
10. Stille, J. K.; Lau, K. S. Y. Acc. Chem. Res. 1977, 10, 434.
11. Suzuki, M.; Oda, Y.; Noyori, R. J. Am. Chem. Soc. 1979, 101, 1623, and references cited therein.
12. The a position of a,βepoxy ketones is highly susceptible toward nucleophilic displacement. See Horstmann, H. In “Methoden der organischen Chemie (Houben-Weyl)”, Bayer, 0., Ed.; Georg Thieme Verlag: Stuttgart, 1977; Vol. VII /2C, Chapter 9, p 2380.
13. Alternatively the hydrogen migration may occur via an 3-ketoenolate-pal-ladium hydride complex formed by -elimination in 3.
14. The accelerating effect by the added dpe ligand is notable, but the exact reason has not yet been elucidated. For related ligand effects on the reactivity of group 8 metal complexes, see: Yoshida, T.; Yamagata, T.; Tulip, T. H.; Ibers, J. A.; Otsuka, S. J. Am. Chem. Soc. 1978, 100, 2063. Dedieu, A.; Hoffmann, R. Alternatively the hydrogen migration may occur via an 3-ketoenolate-pal-ladium hydride complex formed by -elimination in. 1978, 100, 2074.