Allylic C-H acetoxylation with a 4,5-diazafluorenone-ligated palladium catalyst: A ligand-based strategy to achieve aerobic catalytic turnover

Journal of the American Chemical Society

Volumn 132, Issue 43, 2010, Pages 15116-15119

  Campbell, Alison N ^a   White, Paul B ^a   Guzei, Ilia A ^a   Stahl, Shannon S ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETOXYLATION; ANCILLARY LIGANDS; BENZOQUINONES; CATALYTIC TURNOVER; GOOD YIELD; MECHANISTIC STUDIES; OXIDATION REACTIONS; PALLADIUM CATALYST; REDUCTIVE ELIMINATION; STOICHIOMETRIC OXIDANT; TERMINAL ALKENES;

CATALYSIS; CATALYSTS; LIGANDS; OLEFINS; OXIDANTS;

PALLADIUM;

ALKENE; FLUORENONE DERIVATIVE; OXYGEN; PALLADIUM; PALLADIUM COMPLEX;

ACETOXYLATION; AEROBIC METABOLISM; ALLYLATION; ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; ELIMINATION REACTION; HYDRATION; HYDROGEN BOND; ONE POT SYNTHESIS; OXIDATION REDUCTION REACTION; REACTION OPTIMIZATION; STOICHIOMETRY; TURNOVER TIME;

AEROBIOSIS; CARBON; CATALYSIS; FLUORENES; HYDROGEN; LIGANDS; OXYGEN; PALLADIUM;

EID: 78049392925     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja105829t     Document Type: Article

References (65)

1. This subject has been extensively reviewed in recent years. For leading references, see the February 2010 issue of Chemical Reviews.
2. For recent reviews, see: Chen, X., Engle, K. M., Wang, D.-H., and Yu, J.-Q. Angew. Chem., Int. Ed. 2009, 48, 5094-5115
3. Lyons, T. W. and Sanford, M. S. Chem. Rev. 2010, 110, 1147-1169
4. Sun, C.-L., Li, B.-J., and Shi, Z.-J. Chem. Commun. 2010, 46, 677-685
5. III intermediate, whereas in other cases it is not known whether the formal oxidation state of Pd changes. For important leading references, see: Bäckvall, J.-E. and Gogoll, A. Tetrahedron Lett. 1988, 29, 2243-2246
6. Canty, A. J. Acc. Chem. Res. 1992, 25, 83-90
7. Seligson, A. L. and Trogler, W. C. J. Am. Chem. Soc. 1992, 114, 7085-7089
8. Szabó, K. J. Organometallics 1998, 17, 1677-1686
9. Dick, A. R., Kampf, J. W., and Sanford, M. S. J. Am. Chem. Soc. 2005, 127, 12790-12791
10. Giri, R., Chen, X., and Yu, J. Q. Angew. Chem., Int. Ed. 2005, 44, 2112-2115
11. Chen, X., Li, J.-J., Hao, X.-S., Goodhue, C. E., and Yu, J.-Q. J. Am. Chem. Soc. 2006, 128, 78-79
12. Stuart, D. R., Villemure, E., and Fagnou, K. J. Am. Chem. Soc. 2007, 129, 12072-12073
13. Stuart, D. R. and Fagnou, K. Science 2007, 316, 1172-1175
14. Hull, K. L. and Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 9651-9653
15. Lanci, M. P., Remy, M. S., Kaminsky, W., Mayer, J. M., and Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 15618-15620
16. Powers, D. C. and Ritter, T. Nat. Chem. 2009, 1, 302-309
17. Powers, D. C., Geibel, M. A. L., Klein, J. E. M. N., and Ritter, T. J. Am. Chem. Soc. 2009, 131, 17050-17051
18. Khusnutdinova, J. R., Rath, N. P., and Mirica, L. M. J. Am. Chem. Soc. 2010, 132, 7303-7305
19. For advances in Pd-catalyzed aerobic oxidation reactions, see: Stahl, S. S. Angew. Chem., Int. Ed. 2004, 43, 3400-3420
20. Nishimura, T. and Uemura, S. Synlett 2004, 201-216
21. Stoltz, B. M. Chem. Lett. 2004, 33, 362-367
22. Stahl, S. S. Science 2005, 309, 1824-1826
23. Gligorich, K. M. and Sigman, M. S. Chem. Commun. 2009, 3854-3867
24. For a continuous-flow process that enables safe and scalable Pd-catalyzed aerobic oxidations, see: Ye, X., Johnson, M. D., Diao, T., Yates, M. H., and Stahl, S. S. Green Chem. 2010, 12, 1180-1186
25. 2, see: Muzart, J. Chem.-Asian J. 2006, 1, 508-515
26. Stahl, S. S., Thorman, J. L., Nelson, R. C., and Kozee, M. A. J. Am. Chem. Soc. 2001, 123, 7188-7189
27. Konnick, M. M., Guzei, I. A., and Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 10212-10213
28. Konnick, M. M. and Stahl, S. S. J. Am. Chem. Soc. 2008, 130, 5753-5762
29. Popp, B. V. and Stahl, S. S. Chem.-Eur. J. 2009, 15, 2915-2922
30. For example, see: Vargaftik, M. N., Moiseev, I. I., Syrkin, Y. K., Yakshin, V. V., and Lomonosov, M. V. Izv. Akad. Nauk SSSR 1962, 5, 930-931
31. Kitching, W., Rappoport, Z., Winstein, S., and Young, W. G. J. Am. Chem. Soc. 1966, 88, 2054-2055
32. Kikukawa, K., Sakai, K., Asada, K., and Matsuda, T. J. Organomet. Chem. 1974, 77, 131-145
33. Heumann, A. and Åkermark, B. Angew. Chem., Int. Ed. Engl. 1984, 23, 453-454
34. McMurry, J. E. and Kočotovský, P. Tetrahedron Lett. 1984, 25, 4187-4190
35. Jia, C., Müller, P., and Mimoun, H. J. Mol. Catal. A: Chem. 1995, 101, 127-136
36. El Firdoussi, L., Baqqa, A., Allaoud, S., Allal, B. A., Karim, A., Castanet, Y., and Mortreux, A. J. Mol. Catal. A: Chem. 1998, 135, 11-22
37. Grennberg, H. and Bäckvall, J.-E. Chem.-Eur. J. 1998, 4, 1083-1089
38. Attolini, M., Peiffer, G., and Maffei, M. Tetrahedron 2000, 56, 2693-2697
39. Chen, M. S. and White, M. C. J. Am. Chem. Soc. 2004, 126, 1346-1347
40. Chen, M. S., Prabagaran, N., Labenz, N. A., and White, M. C. J. Am. Chem. Soc. 2005, 127, 6970-6971
41. Mitsudome, T., Umetani, T., Nosaka, N., Mori, K., Mizugaki, T., Ebitani, K., and Kaneda, K. Angew. Chem., Int. Ed. 2006, 45, 481-485
42. Lin, B.-L., Labinger, J. A., and Bercaw, J. E. Can. J. Chem. 2009, 87, 264-271
43. Pilarski, L. T., Selander, N., Böse, D., and Szabó, K. J. Org. Lett. 2009, 11, 5518-5521
44. Henderson, W. H., Check, C. T., Proust, N., and Stambuli, J. P. Org. Lett. 2010, 12, 824-827
45. Thiery, E., Aouf, C., Belloy, J., Harakat, D., Le Bras, J., and Muzart, J. J. Org. Chem. 2010, 75, 1771-1774
46. For leading references to other advances in Pd-catalyzed allylic C-H oxidation, see: Fraunhoffer, K. J. and White, M. C. J. Am. Chem. Soc. 2007, 129, 7274-7276
47. Liu, G., Yin, G., and Wu, L. Angew. Chem., Int. Ed. 2008, 47, 4733-4736
48. Vermeulen, N. A., Delcamp, J. H., and White, M. C. J. Am. Chem. Soc. 2010, 132, 11323-11328
49. Yin, G., Wu, Y., and Liu, G. J. Am. Chem. Soc. 2010, 132, 11978-11987
50. Grennberg, H., Gogoll, A., and Bäckvall, J.-E. Organometallics 1993, 12, 1790-1793
51. For example, see: Nishimura, T., Onoue, T., Ohe, K., and Uemura, S. Tetrahedron Lett. 1998, 39, 6011-6014
52. Fix, S. R., Brice, J. L., and Stahl, S. S. Angew. Chem., Int. Ed. 2002, 41, 164-166
53. Nishimura, T., Araki, H., Maeda, Y., and Uemura, S. Org. Lett. 2003, 5, 2997-2999
54. Andappan, M. M. S., Nilsson, P., and Larhed, M. Chem. Commun. 2004, 218-219
55. Sheldon, R. A., Arends, I. W. C. E., ten Brink, G.-J., and Dijksman, A. Acc. Chem. Res. 2002, 35, 774-781
56. Yoo, K. S., Park, C. P., Yoon, C. H., Sakaguchi, S., O'Neill, J., and Jung, K. W. Org. Lett. 2007, 9, 3933-3935
57. Zhang, Y.-H., Shi, B.-F., and Yu, J.-Q. J. Am. Chem. Soc. 2009, 131, 5072-5074
58. Haggin, J. Chem. Eng. News 1993, 71 (22) 23-27
59. Beller, M., Seayad, J., Tillack, A., and Jiao, H. Angew. Chem., Int. Ed. 2004, 43, 3368-3398
60. 2 in solution.
61. 2 species. Separately, it was noted that the reaction of 4 was unaffected by the presence of excess ligand 1 (5 equiv) in solution, suggesting that formation of allyl acetate does not proceed via pre-equilibrium dissociation of 1 from the Pd center.
62. 2 was not reported. Preliminary studies have suggested that (bpm)Pd(allyl) complexes react differently under our conditions. Further work will be needed to make a direct comparison between ligand 1 and bipyrimidine in allylic acetoxylation reactions.
63. - salts of 4 and 5 were characterized by X-ray crystallography. For a summary of the structural data, see Figure S6 and the additional data in the Supporting Information.
64. 2- peroxo species relevant to this process. See ref 6b and: Popp, B. V., Thorman, J. L., and Stahl, S. S. J. Mol. Catal. A: Chem. 2006, 251, 2-7
65. Popp, B. V., Morales, C. M., Landis, C. R., and Stahl, S. S. Inorg. Chem. 2010, 49, 8200-8207