Apparent Syn Elimination of Palladium Oxide from a β-Hydroxy Organopalladium Intermediate

Organometallics

Volumn 2, Issue 6, 1983, Pages 772-775

  Hacksell, Uli ^a   Daves, G Doyle ^a  

^a LEHIGH UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001269314     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om00078a017     Document Type: Article

References (23)

1. (a) Heck, R. F. J. Ám. Chem. Soc. 1968, 90, 5526. (b) Melpolder, J. B.; Heck, R. F. J. Org. Chem. 1976, 41, 265. (c) Chalk, A. J.; Magennis, S. A. J. Org. Chem. 1976, 41, 273. (d) Von Werner, K. J. Organomet. Chem. 1977, 136, 385. (e) Tamaru, Y.; Yamada, Y.; Yoshida, Z.-I. Tetrahedron Lett. 1977, 3365. (f) Tamaru, Y.; Yamada, Y.; Yoshida, Z.-I. J. Org. Chem. 1978, 43, 3396. (g) Patel, B. A.; Heck, R. F. J. Org. Chem. 1978, 43, 3898. (h) Tamaru, Y.; Yamada, Y.; Yoshida, Z.-I. Tetrahedron 1979, 35, 329. (i) Smadja, W.; Czernecki, S.; Ville, G.; Georgoulis, C. Tetrahedron Lett. 1981, 22, 2479. (j) Kao, L.-C; Stakem, F. G.; Patel, B. A.; Heck, R. F. J. Org. Chem. 1982, 47, 1267.
2. For general reviews see: Henry, P. M. “Palladium Catalyzed Oxidation of Hydrocarbons”; Klewer Boston, Inc.: Boston, Mass, 1980. Collman, J. P.; Hegedus, L. S. “Principles and Applications of Organotransition Metal Chemistry”; University Science Books: Mill Valley, Calif., 1980. Tsuji, J. “Organic Synthesis with Palladium Compounds”; Springer-Verlag: Berlin, 1980. Heck, R. F. “Organotransition Metal Chemistry”; Academic Press: New York, 1974.
3. (a) Arai, I.; Daves, G. D., Jr. J. Am. Chem. Soc. 1981, 103, 7683. (b) Arai, I.; Lee, T. D.; Hanna, R.; Daves, G. D., Jr. Organometallics 1982, 1, 742.
4. (a) Báckvall, J. E.; Åkermark, B.; Ljunggren, S. O. J. Am. Chem. Soc. 1979, 101, 2411. (b) Åkermark, B.; Báckvall, J. E.; Zetterberg, K. Acta Chem. Scand., Ser. B 1982, B36, 577.
5. Arai, I.; Daves, G. D., Jr. J. Am. Chem. Soc. 1978, 100, 287; J. Org. Chem. 1978, 43, 4110.
6. (a) Daves, G. D., Jr.; Cheng, C. C. Prog. Med. Chem. 1976, 13, 303. (b) Hannessian, S.; Pernet, A. G. Ado. Carbohydr. Chem. Biochem. 1976, 3, 111. (c) Fox, J. J.; Watanabe, K. A.; Klein, R. S.; Chu, C. K.; Tam, S. Y.-K.; Reichman, U.; Hirota, K.; Wempen, I.; Lopez, C.; Burchenal, J. H. Colloq.-Inst. Natl. Sante Rech. Med. 1978, 81, 241.
7. (a) Ireland, R. E.; Wilcox, C. S.; Thaisrivonga, S. J. Org. Chem. 1978, 43, 786. (b) Ireland, R. E.; Thaierivongs, S.; Vanier, N.; Wilcox, C. S. J. Org. Chem. 1980, 45, 48.
8. All the compounde reported exhibit 1H, 13C NMR, and mass spectra in agreement with the assigned structures. For convenience, we use the commnn carbohydrate numbering system (the anomeric carbon is designated 10 in discussions of spectra and structural features.
9. Barfield, M.; Spear, R. J.; Sternhell, S. J. Am. Chem. Soc. 1975, 97, 5160 and references cited therein.
10. J1′H, 4′H has been reported as -1.5 Hz for 2′,3′-didehydro-2′,3′-dideoxy-l-methyl-5′-0-trityl-(3-pseudouridine in which the 1′ and 4′ substituents are cis. Matsuda, A.; Chu, C. K.; Reichman, U.; Pankiewicz, K.; Watanabe, K. A.; Fox, J. J. J. Org. Chem. 1981, 46, 3603.
11. The relative configurations at C1′, C2′, C3′, and C4′ of 5 and 6 was determined by using well-documented empirical rules that correlate chemical shifts in 1H and 13C NMR of the isopropylidene unit with the α or β configuration of nucleosides. See, e.g.: (a) Imbach, J. L. An. N.Y. Acad. Sci. 1975, 255, 177. (b) Ohrui, H.; Jones, G. H.; Moffat, J. G.; Maddox, M. L.; Christensen, A. T.; Byram, S. K. J. Am. Chem. Soc. 1975, 97, 4602. (c) Cousineau, T. J.; Secrist, J. A., Ill J. Org. Chem. 1979, 24, 4351.
12. Prepared from α-pseudouridine (Sigma) using dimethylformamide dimethyl acetal according to: Hirota, K.; Watanabe, K. A.; Fox, J. J. J. Heterocycl. Chem. 1977, 14, 537.
13. Mass spectra (fast atom bombardment) of the crude reaction mixture containing adduct 3 exhibit ion clusters at m/z 446 (106Pd isotope) corresponding to (a) [3a-LOAc]+ or (b) [3b-L+H+]+. In mass spectrometry using a soft ionization technique observed ions are preformed (a) or formed by protonation (b); as a result, no distinction between structures 3a and 3b is possible (see: Cotter, R. J. Anal. Chem. 1980, 52, 1589A. Daves, G. D., Jr. Acc. Chem. Res. 1979, 12, 359).
14. All additions of organopalladium reagents to double bonds which have been carefully examined have been shown to be syn; no example of anti addition of a carbon σ-bonded palladium reagent is known (See: Henry, P. M.; Ward, G. A. J. Am. Chem. Soc. 1972, 94, 673 and ref 2 and 4). In our closely related studies using pyranoid glycals3 syn addition of the palladium reagent derived from 2 has been established conclusively.
15. The unlikely possibility that 4 arises via a (t)3-allyl)palladium complex derived from 1 is ruled out by the establishment that the intermediate adduct (3) possesses both carbon bound oxygen at C-3 and palladium. For relevant studies of (ij3-allyl)palladium chemistry see: Trost, B. M. Pure Appl. Chem. 1981, 53, 2357. Matsushita, H.; Negishi, E. J. Chem. Soc., Chem. Commun. 1982, 160. Dunkerton, L. V.; Serino, A. J. J. Org. Chem. 1982, 47, 2812. Similarly, the possibilities that 4 arises from 3a by (a) hydroxyl acetylation and subsequent syn elimination of palladium acetate (suggested by a reviewer) or (b) hydroxyl displacement by acetate followed by anti elimination of palladium acetate appear remote since mass spectrometry15 and reduction of crude reaction mixtures indicate the presence of 3a but provide no evidence for an acetoxy analogue. Addition (but not elimination) of acetate syn to palladium in η3-alkyl complexation has been observed: Báckvall, J. E.; Nordberg, R. E. J. Am. Chem. Soc. 1981, 103, 4959. Trost, B. M.; Verhoeven, T. R. J. Am. Chem. Soc. 1980, 102, 4730.
16. Compare ref 4. See, however: Gregor, N.; Henry, P. M. J. Am. Chem. Soc. 1981, 103, 681. Wan, W. K.; Zaw, K.; Henry, P. M. J. Mol. Catal. 1982, 16, 81.
17. Sharpless, K. B.; Teranishi, A. Y.; Báckvall, J.-E. J. Am. Chem. Soc. 1977, 99, 3120.
18. Andrews, M. A.; Cheng, C.-W.F. J. Am. Chem. Soc. 1982, 104, 4268.
19. Schlodder, R.; Ibers, J. A.; Lenarda, M.; Graziani, M. J. Am. Chem. Soc. 1974, 96, 6893.
20. Vedejs, E.; Snoble, K. A. J. J. Am. Chem. Soc. 1973, 95, 5778.
21. Corey, E. J.; Durst, T. J. Am. Chem. Soc. 1968, 90, 5548.
22. Hudrlik, P. F.; Peterson, D.; Roña, R. J. J. Org. Chem. 1975, 40, 2263.
23. Kauffmann, T.; Kriegesmann, R.; Hamsen, A. Chem. Ber. 1982, 115, 1818.