Structural features and reactivity of (sparteine)PdCl2: A model for selectivity in the oxidative kinetic resolution of secondary alcohols

Journal of the American Chemical Society

Volumn 130, Issue 47, 2008, Pages 15957-15966

  Trend, Raissa M ^a   Stoltz, Brian M ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DERIVATIVES; KETONES; LIGANDS; ORGANIC COMPOUNDS; PALLADIUM;

ALKOXIDES; CHIRAL LIGANDS; DIASTEREOMERS; ENANTIOSELECTIVE OXIDATIONS; KEY FEATURES; KINETIC RESOLUTIONS; METAL CENTERS; OXIDATIVE KINETIC RESOLUTIONS; PYRIDINE DERIVATIVES; SECONDARY ALCOHOLS; STRUCTURAL FEATURES; STRUCTURAL STUDIES;

PYRIDINE;

CHLORIDE; OXIDOREDUCTASE; PALLADIUM; PALLADIUM CHLORIDE; PYRIDINE; PYRIDINE DERIVATIVE; SPARTEINE; UNCLASSIFIED DRUG;

ALCOHOL OXIDATION; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRALITY; DIASTEREOISOMER; ENANTIOMER; ENANTIOSELECTIVITY; LIGAND BINDING; OXIDATION KINETICS; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; STEREOMETRY; STRUCTURE ACTIVITY RELATION; SUBSTITUTION REACTION; SYNTHESIS;

ALCOHOLS; HYDROGEN; ISOMERISM; KINETICS; LIGANDS; MODELS, CHEMICAL; MODELS, MOLECULAR; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; OXIDATION-REDUCTION; PYRIDINES; STEREOISOMERISM;

EID: 56749149527     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja804955e     Document Type: Article

References (79)

1. Wieland, H. Ber. Dtsch. Chem. Ges. 1912, 45, 484-493.
2. Schwartz, J.; Blackburn, T. F. J. Chem. Soc., Chem. Commun. 1977, 157-158.
3. For recent Pd(II) aerobic alcohol oxidations, see: (a) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185-3189.
4. (b) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750-6755.
5. (c) Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636-1639.
6. (d) For a review, see: Muzart, J. Tetrahedron 2003, 59, 5789-5816.
7. (a) Ferreira, E. M.; Stoltz, B. M. J. Am. Chem. Soc. 2001, 123, 7725-7726.
8. (b) Bagdanoff, J. T.; Ferreira, E. M.; Stoltz, B. M. Org. Lett. 2003, 5, 835-837.
9. (c) For conditions employing chloroform and air, see: Bagdanoff, J. T.; Stoltz, B. M. Angew. Chem., Int. Ed. 2004, 43, 353-357.
10. For a similar system, see: (a) Jensen, D. R.; Pugsley, J. S.; Sigman, M. S. J. Am. Chem. Soc. 2001, 123, 7475-7476.
11. (b) Mueller, J. A.; Jensen, D. R.; Sigman, M. S. J. Am. Chem. Soc. 2002, 124, 8202-8203.
12. (c) Jensen, D. R.; Sigman, M. S. Org. Lett. 2003, 5, 63-65.
13. (d) Mandal, S. K.; Jensen, D. R.; Pugsley, J. S.; Sigman, M. S. J. Org. Chem. 2003, 68, 4600-4603.
14. (e) Mueller, J. A.; Sigman, M. S. J. Am. Chem. Soc. 2003, 125, 7005-7013.
15. (f) Mandal, S. K.; Sigman, M. S. J. Org. Chem. 2003, 68, 7535-7537.
16. Mueller, J. A.; Cowell, A.; Chandler, B. D.; Sigman, M. S. J. Am. Chem. Soc. 2005, 127, 14817-14824.
17. Trend, R. M.; Stoltz, B. M. J. Am. Chem. Soc. 2004, 126, 4482-4483.
18. Nielsen, R. J.; Keith, J. M.; Stoltz, B. M.; Goddard, W. A. J. Am. Chem. Soc. 2004, 126, 7967-7974.
19. rel = ln[(1- C)(1 -ee)]/ln[(1- C)(1 + ee)], where C is conversion and ee is enantiomeric excess.
20. Caspi, D. D.; Ebner, D. C.; Bagdanoff, J. T.; Stoltz, B. M. Adv. Synth. Catal. 2004, 346, 185-189.
21. O'Brien and co-workers have synthesized analogues of (+)-sparteine that are somewhat effective as sparteine surrogates, see: (a) Dearden, M. J.; Firkin, C. R.; Hermet, J.-P. R.; O'Brien, P. J. Am. Chem. Soc. 2002, 124, 11870-11871.
22. (b) Hermet, J.-P. R.; Porter, D. W.; Dearden, M. J.; Harrison, J. R.; Koplin, T.; O'Brien, P.; Parmene, J.; Tyurin, V.; Whitwood, A. C.; Gilday, J.; Smith, N. M. Org. Biomol. Chem. 2003, 1, 3977-3988.
23. (c) Dearden, M. J.; McGrath, M. J.; O'Brien, P. J. Org. Chem. 2004, 69, 5789-5792.
24. (d) Ebner, D. C.; Trend, R. M.; Genet, C.; McGrath, M. J.; O'Brien, P.; Stoltz, B. M. Angew. Chem., Int. Ed. 2008, 47, 6367-6370.
25. 2 has recently been reported, with moderate levels of selectivity: Chen, T.; Jiang, J.-J.; Xu, Q.; Shi, M. Org. Lett. 2007, 9, 865-868.
26. (a) Sheldon, R. A.; Arends, I. W. C. E. In Advances in Catalytic Activation of Dioxygen by Metal Complexes; Simándi, L. I., Ed.; Kluwer: Dordrecht; 2003; Vol. 26,Chap. 3, p 123.
27. (b) Steinhoff, B. A.; Stahl, S. S. Org. Lett. 2002, 4, 4179-4181.
28. (c) Stahl, S. S.; Thorman, J. L.; Nelson, R. C.; Kozee, M. A. J. Am. Chem. Soc. 2001, 123, 7188-7189, and references therein.
29. For another example that uses similar logic for (-)-sparteine, see: Li, X.; Schenkel, L. B.; Kozlowski, M. C. Org. Lett. 2000, 2, 875-878.
30. Kagan, H. B.; Dang, T.-P. J. Am. Chem. Soc. 1972, 94, 6429-6433.
31. Whitesell, J. K. Chem. Rev. 1989, 89, 1581-1590.
32. Structure originally reported in ref 3a.
33. Leonard, N. J. In The Alkaloids, Chemistry and Physiology, Vol. III; Manske, R. H. F., Holmes, H. L., Eds.; Academic Press: New York, 1953; pp 119-199.
34. The same product was observed in the reaction of the chloro-bridged dimer with 2.0 equiv of pyridine in 91% yield. (Chemical Equation Presented)
35. Two molecules were found in the asymmetric unit. See Supporting Information for further details.
36. For examples that possess β-hydrogen atoms, see: (a) Bouquillon, S.; du Moullinet d'Hardemare, A.; Averbuch-Pouchot, M.-T.; Benin, F.; Muzart, J.; Durif, M. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1999, 55, 2028-2030.
37. (b) Achtembosch, M.; Klufers, P. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1994, 50, 175-178.
38. (c) Hubel, R.; Polbom, K.; Beck, W. Eur. J. Inorg. Chem. 1999, 471-482.
39. (d) Kapteijn, G. M.; Grove, D. M.; van Koten, G.; Smeets, W. J. J.; Spek, A. L. Inorg. Chim. Acta 1993, 207, 131-134.
40. (e) Klufers, P.; Kunte, T. Angew. Chem., Int. Ed. 2001, 40, 4210-4212.
41. (f) Kastele, X.; Klufers, P.; Kunte, T. Z. Anorg. Allg. Chem. 2001, 627, 2042-2044.
42. (g) Kapteijn, G. M.; Baesjou, P.; Alsters, P. L.; Grove, D. M.; Smeets, W. J. J.; Kooijman, H.; Spek, A. L.; van Koten, G. Chem. Ber. 1997, 130, 35-44.
43. (h) Kapteijn, G. M.; Dervisi, A.; Grove, D. M.; Kooijman, H.; Lakin, M. T.; Spek, A. L.; van Koten, G. J. Am. Chem. Soc. 1995, 117, 10939-10949.
44. (i) Ahlrichs, R.; Ballauff, M.; Eichkom, K.; Hanemann, O.; Kettenbach, G.; Klufers, P. Chem.-Eur. J. 1998, 4, 835-844.
45. (j) Klufers, P.; Kunte, T. Eur. J. Inorg. Chem. 2002, 1285-1289.
46. 3). See: Kim, Y.-J.; Osakada, K.; Takenaka, A.; Yamamoto, A. J. Am. Chem. Soc. 1990, 112, 1096-1104.
47. 1H NMR using an internal standard; see Supporting Information.
48. Another possibility is that the thermodynamics of solubility play a role.
49. While the structural studies we have undertaken have been almost exclusively in the solid state, the consistency of the results and the support of theoretical calculations give us confidence in our model.
50. (a) Bryndza, H. E.; Tam, W. Chem. Rev. 1988, 88, 1163-1188.
51. (b) Zhao, J.; Hesslink, H.; Hartwig, J. F. J. Am. Chem. Soc. 2001, 123, 7220-7227.
52. (c) For an alternative with platinum, see: Bryndza, H. E.; Calabrese, J. C.; Marsi, M.; Roe, D. C.; Tam, W.; Bercaw, J. E. J. Am. Chem. Soc. 1986, 108, 4805-4813.
53. Thorn, D. L.; Hoffmann, R. J. Am. Chem. Soc. 1978, 100, 2079-2090.
54. For references pertaining to a-isosparteine, see: (a) Winterfeld, K. Arch. Pharm. 1928, 266, 299-325.
55. (b) Marion, L.; Turcotte, F.; Ouellet, J. Can. J. Chem. 1951, 29, 22-29.
56. (c) Galinovsky, F.; Knoth, P.; Fischer, W. Monatsh. Chem. 1955, 86, 1014-1023.
57. (d) Leonard, N. J.; Thomas, P. D.; Gash, V. W. J. Am. Chem. Soc. 1955, 77, 1552-1558.
58. (e) Oinuma, H.; Dan, S.; Kakisawa, H. J. Chem. Soc., Chem. Commun. 1983, 654-655.
59. (f) Blakemore, P. R.; Kilner, C.; Norcross, N. R.; Astles, P. C. Org. Lett. 2005, 7, 4721-4724.
60. (g) Przybylska, M.; Barnes, W. H. Acta Crystallogr. 1953, 6, 377-384.
61. For references pertaining to β-isosparteine, see: (a) Greenhalgh, R.; Marion, L. Can. J. Chem. 1956, 34, 456-458.
62. (b) Carmack, M.; Douglas, B.; Martin, E. W.; Suss, H. J. Am. Chem. Soc. 1955, 77, 4435.
63. (c) Carmack, M.; Goldberg, S. I.; Martin, E. W. J. Org. Chem. 1967, 32, 3045-3049.
64. (d) Wanner, M. J.; Koomen, G.-J. J. Org. Chem. 1996, 61, 5581-5586.
65. (e) Childers, L. S.; Folting, K., Jr.; Streib, W. E. Acta Crystallogr. 1975, B31, 924-925.
66. Leonard, N. J.; Beyler, R. E. J. Am. Chem. Soc. 1950, 72, 1316-1323.
67. Winterfeld, K.; Bange, H.; Lalvani, K. S. Justus Liebigs Ann. Chem. 1966, 698, 230-234.
68. Although the sign of rotation is different than for (-)-sparteine (1) and (-)-α-isosparteine (47), it is in the same enantiomeric series.
69. Cesium carbonate (along with excess (-)-sparteine) is a component of the "rate-accelerated" conditions for oxidative kinetic resolution.
70. 2 (14) without added ligand was also diminished, we believe this is a result of (-)-sparteine (1) decomplexation in the absence of excess ligand.
71. 1-symmetric ligand in asymmetric processes: (a) Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. Chem. Rev. 2000, 100, 1253.
72. (b) Helmchen, G.; Pfaltz, A. Acc. Chem. Res. 2000, 33, 336.
73. (c) Williams, J. M. J. Synlen 1996, 705.
74. (d) Hatano, M.; Tamanaka, M.; Mikami, K. Eur. J. Org. Chem. 2003, 2552.
75. (e) Nozaki, K.; Komaki, H.; Kawashima, Y.; Hiyama, T.; Matsubara, T. J. Am. Chem. Soc. 2001, 123, 534.
76. (f) Kocovsky, P.; Vyskocil, S.; Smrcina, M. Chem. Rev. 2003, 103, 3213.
77. (g) Bolm, C.; Verruci, M.; Simic, O.; Cozzi, P. G.; Raabe, G.; Okamura, H. Chem. Commun. 2003, 2826.
78. (h) Ohashi, A.; Kikuchi, S.-i.; Yasutake, M.; Imamoto, T. Eur. J. Org. Chem. 2002, 2535.
79. (i) Hoge, G.; Wu, H.-P.; Kissel, W. S.; Pflum, D. A.; Greene, D. J.; Bao, J. J. Am. Chem. Soc. 2004, 126, 5966.