Ligand-modulated palladium oxidation catalysis: Mechanistic insights into aerobic alcohol oxidation with the Pd(OAc)2/pyridine catalyst system

Organic Letters

Volumn 4, Issue 23, 2002, Pages 4179-4181

  Steinhoff, Bradley A ^a   Stahl, Shannon S ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

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ARTICLE;

EID: 0012253713     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol026988e     Document Type: Article

References (31)

1. For leading references, see: Sheldon, R. A.; Arends, I. W. C. E.; Dijksman, A. Catal. Today 2000, 57, 157-166.
2. (a) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011-6014.
3. (b) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750-6755.
4. (a) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157-158.
5. (b) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097-7098.
6. (c) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185-3189.
7. (d) Bortolo, R.; Bianchi, D.; D'Aloisio, R.; Querci, C.; Ricci, M. J. Mol. Catal. A 2000, 153, 25-29.
8. (e) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636-1639.
9. (f) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260-263.
10. (g) Jensen, D. R.; Pugsley, J. S.; Sigman, M. S. J. Am. Chem. Soc. 2001, 123, 7475-7476.
11. (h) Ferreira, E. M.; Stoltz, B. M. J. Am. Chem. Soc. 2001, 123, 7725-7726.
12. (a) Stahl, S. S.; Thorman, J. L.; Nelson, R. C.; Kozee, M. A. J. Am. Chem. Soc. 2001, 123, 7188-7189.
13. (b) Steinhoff, B. A.; Fix, S. R.; Stahl, S. S. J. Am. Chem. Soc. 2002, 124, 766-767.
14. Similar catalyst systems have been employed in other oxidative transformations. (a) Oxidative ring opening of tert-cyclobutanols: Nishimura, T.; Ohe, K.; Uemura, S. J. Org. Chem. 2001, 66, 1455-1465.
15. (b) Intramolecular oxidative amination of olefins: Fix, S. R.; Brice, J. L.; Stahl, S. S. Angew. Chem., Int. Ed. 2002, 41, 164-166.
16. 2: Mueller, J. A.; Jensen, D. R.; Sigman, M. S. J. Am. Chem. Soc. 2002, 124, 8202-8203.
17. 2: ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Adv. Synth. Catal. 2002, 344, 355-369.
18. Kravtsova, S. V.; Romm, I. P.; Stash, A. I.; Belsky, V. K. Acta Crystallogr. Sect. C 1996, 52, 2201-2204.
19. -1 for display in Figure 1. Reaction parameters are included in the figure caption.
20. The stoichiometric reaction was carried out at 80 °C with a 1:1 substrate:palladium ratio.
21. The catalyst appears to have enhanced stability at higher pyridine:palladium ratios based on the absence of palladium black at longer reaction times. The synthetically optimized ratio of 4:1 probably reflects a balance between optimal turnover rates and catalyst lifetime.
22. For metal-alkyl β-hydride elimination reactions, see: (a) Whitesides, G. M.; Gaasch, J. F.; Stedronsky, E. R. J. Am. Chem. Soc. 1972, 94, 5258-5270.
23. (b) Romeo, R.; Alibrandi, G.; Scolaro, L. M. Inorg. Chem. 1993, 32, 4688-4694.
24. (c) Goj, L. A.; Widenhoefer, R. A. J. Am. Chem. Soc. 2001, 123, 11133-11147.
25. (d) Shultz, L. H.; Brookhart, M. Organometallics 2001, 20, 3975-3982.
26. For an iridium(I)-alkoxide β-hydride elimination reaction, see: Zhao, J.; Hesslink, H.; Hartwig, J. F. J. Am. Chem. Soc. 2001, 123, 7220-7227.
27. 8-complexes has also been observed. See: (a) Ozawa, F.; Ito, T.; Yamamoto, A. J. Am. Chem. Soc. 1980, 102, 6457-6463.
28. (b) Bryndza, H. E.; Calabrese, J. C.; Marsi, M.; Roe, D. C.; Tam, W.; Bercaw, J. E. J. Am. Chem. Soc. 1986, 108, 4805-4813.
29. (c) Alibrandi, G.; Cusumano, M.; Minniti, D.; Scolaro, L. M.; Romeo, R. Inorg. Chem. 1989, 28, 342-347.
30. The [Pd]-dependence under conditions of constant (excess) [py] also reveals a nonlinear dependence, although the curvature is substantially less than that in Figure 1C. The precise origin of this effect is presently being investigated; it may reflect slow palladium decomposition during the reaction or the presence of a multinuclear (i.e., ≥2) catalyst resting state. The results of these studies will be reported in a forthcoming full report.
31. van Leeuwen, P. W. N. M. Appl. Catal. A-Gen. 2001, 212, 61-81.