Terminal olefins to linear α,β-unsaturated ketones: Pd(II)/hypervalent iodine co-catalyzed wacker oxidation-dehydrogenation

Journal of the American Chemical Society

Volumn 135, Issue 21, 2013, Pages 7831-7834

  Bigi, Marinus A ^a   White, M Christina ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COCATALYST; HYPERVALENT IODINE; STOICHIOMETRIC OXIDANT; TERMINAL OLEFINS; UNSATURATED KETONES;

CATALYSIS; DEHYDROGENATION; FUNCTIONAL GROUPS; IODINE; KETONES; OLEFINS;

PALLADIUM COMPOUNDS;

ALKENE; ALKYL GROUP; ALPHA,BETA UNSATURATED KETONE DERIVATIVE; FUNCTIONAL GROUP; IODINE; KETONE; PALLADIUM; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; OXIDATIVE DEHYDROGENATION; STEREOCHEMISTRY; STOICHIOMETRY;

ALKENES; CATALYSIS; HYDROGEN; KETONES; OXIDATION-REDUCTION; PALLADIUM;

EID: 84878387862     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja402651q     Document Type: Article

References (52)

1. Crabtree, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437
2. Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507
3. Dick, A. R.; Sanford, M. S. Tetrahedron 2006, 62, 2439
4. Giri, R.; Shi, B.-F.; Engle, K. M.; Maugel, N.; Yu, J.-Q. Chem. Soc. Rev. 2009, 38, 3242
5. White, M. C. Science 2012, 335, 807
6. White, M. C. Synlett 2012, 23, 2746
7. Hinman, A.; Du Bois, J. J. Am. Chem. Soc. 2003, 125, 11510
8. Wender, P. A.; Hilinski, M. K.; Mayweg, A. V. W. Org. Lett. 2005, 7, 79
9. Fraunhoffer, K. J.; Bachovchin, D. A.; White, M. C. Org. Lett. 2005, 7, 223
10. Covell, D. J.; Vermeulen, N. A.; Labenz, N. A.; White, M. C. Angew. Chem., Int. Ed. 2006, 45, 8217
11. Stang, E. M.; White, M. C. Nat. Chem. 2009, 1, 547
12. Vermeulen, N. A.; Delcamp, J. H.; White, M. C. J. Am. Chem. Soc. 2010, 132, 11323
13. Weiner, B.; Baeza, A.; Jerphagnon, T.; Feringa, B. L. J. Am. Chem. Soc. 2009, 131, 9473
14. Michel, B. W.; McCombs, J. R.; Winkler, A.; Sigman, M. S. Angew. Chem., Int. Ed. 2010, 131, 9473
15. Keith, J. A.; Henry, P. M. Angew. Chem., Int. Ed. 2009, 48, 9038
16. Chen, M. S.; White, M. C. J. Am. Chem. Soc. 2004, 126, 1346
17. Vermeulen, N. A.; Delcamp, J. H. J. Am. Chem. Soc. 2010, 132, 11323
18. Gormisky, P. E.; White, M. C. J. Am. Chem. Soc. 2011, 133, 12584
19. Fraunhoffer, K. J.; White, M. C. J. Am. Chem. Soc. 2007, 129, 7274
20. Reed, S. A.; White, M. C. J. Am. Chem. Soc. 2008, 130, 3316
21. Young, A. J.; White, M. C. J. Am. Chem. Soc. 2008, 130, 14090
22. Stang, E. M.; White, M. C. J. Am. Chem. Soc. 2011, 133, 14892
23. Reich, H. J.; Wollowitz, S. Org. React. 1993, 44, 1
24. Trost, B. M. Chem. Rev. 1978, 78, 363
25. Ito, Y.; Hirao, T.; Saegusa, T. J. Org. Chem. 1978, 43, 1011
26. Larock, R. C.; Hightower, T. R.; Kraus, G. A.; Hahn, P.; Zheng, D. Tetrahedron Lett. 1995, 36, 2423
27. Yu, J. Q.; Wu, H. C.; Corey, E. J. Org. Lett. 2005, 7, 1415
28. Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863
29. Walker, D.; Hiebert, J. D. Chem. Rev. 1967, 67, 153
30. Nicolaou, K. C.; Zhong, Y.-L.; Baran, P. S. J. Am. Chem. Soc. 2000, 122, 7596
31. Nicolaou, K. C.; Montagnon, T.; Baran, P. S.; Zhong, Y.-L. J. Am. Chem. Soc. 2002, 124, 2245
32. Nicolaou, K. C.; Montagnon, T.; Baran, P. S. Angew. Chem., Int. Ed. 2002, 41, 993
33. Uyanik, M.; Akakura, M.; Ishihara, K. J. Am. Chem. Soc. 2009, 131, 251
34. Dobereiner, G. E.; Crabtree, R. H. Chem. Rev. 2010, 110, 681
35. Choi, J.; MacArthur, A. H. R.; Brookhart, M.; Goldman, A. S. Chem. Rev. 2011, 111, 1761
36. Muzart, J. Eur. J. Org. Chem. 2010, 3779
37. Theissen, R. J. J. Org. Chem. 1971, 36, 752
38. Muzart, J.; Pete, J. P. J. Mol. Catal. 1982, 15, 373
39. Izawa, Y.; Pun, D.; Stahl, S. S. Science 2011, 333, 209
40. Diao, T.; Stahl, S. S. J. Am. Chem. Soc. 2011, 133, 14566
41. Diao, T.; Wadzinski, T. J.; Stahl, S. S. Chem. Sci. 2012, 3, 887
42. Gao, W.; He, Z.; Qian, Y.; Zhao, J. Chem. Sci. 2012, 3, 883
43. Tokunaga, M.; Harada, S.; Iwasawa, T.; Obora, Y.; Tsuji, Y. Tetrahedron Lett. 2007, 48, 6860
44. For a rare example of Ir-catalyzed dehydrogenation of cyclic ketones, see: Zhang, X. W.; Wang, D. Y.; Emge, T. J.; Goldman, A. S. Inorg. Chim. Acta 2011, 369, 253
45. Zhu, J.; Liu, J.; Ma, R. Q.; Xie, H. X.; Li, J.; Jiang, H. L.; Wang, W. Adv. Synth. Catal. 2009, 351, 1229
46. Liu, J.; Zhu, J.; Jiang, H. L.; Wang, W.; Li, J. Chem.-Asian J. 2009, 4, 1712
47. Zhdankin, V. V.; Stang, P. J. Chem. Rev. 2008, 108, 5299
48. Moriarty, R. M.; Prakash, O. Org. React. 1999, 54, 273
49. Koser, G. F. In Hypervalent Iodine Chemistry: Modern Developments in Organic Synthesis; Wirth, T., Ed.; Springer, 2003; p 137.
50. Merritt, E. A.; Olofsson, B. Synthesis 2011, 517
51. Based on the well-precedented ability of hypervalent iodine reagents to oxidize organopalladium(II) intermediates, we considered the possibility of initial generation of a Pd(II) enolate followed by oxidation with the I(III)-based oxidant to provide a higher valent Pd(IV) enolate, with release of PhI (for a review, see: Deprez, N. R.; Sanford, M. S. Inorg. Chem. 2007, 46, 1924). Alternatively, as proposed in Figure 1, an iodonium(III) enolate might undergo reductive displacement with Pd(0), affording a Pd(II) enolate and PhI. In either case, β-hydride elimination from a Pd enolate would release product, and the I(III) reagent would function as a terminal oxidant. We disfavor both pathways because we have never observed PhI, the reaction requires stoichiometric 1,4-BQ, and I(III) reagents can be used substoichiometrically
52. A mechanism that cannot be excluded is iodonium(III) enolate formation (Figure 1) followed by a σ-bond metathesis with Pd(II) to furnish a Pd(II)-enolate with no change in the oxidation state of the palladium or iodine. Examples of σ-bond metathesis have been proposed for silyl enol ethers with I(III) reagents: Chen, K.; Koser, G. F. J. Org. Chem. 1991, 56, 5764