Unexpected TiIII/Mn-promoted pinacol coupling of ketones

Journal of Organic Chemistry

Volumn 74, Issue 9, 2009, Pages 3616-3619

  Paradas, Miguel ^a   Campaña, Araceli G ^a   Estévez, Rosa E ^a   De Cienfuegos, Luis Álvarez ^a   Jiménez, Tania ^a   Robles, Rafael ^a   Cuerva, Juan M ^a   Oltra, J Enrique ^a  

^a UNIVERSITY OF GRANADA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC KETONES; C-C BOND FORMING REACTION; INDISPENSABLE TOOLS; INTRAMOLECULAR PROCESS; LEWIS ACID; NEW APPLICATIONS; PINACOL; REACTION CONDITIONS; STARTING MATERIALS; STEREOSELECTIVE SYNTHESIS; TITANOCENE; VICINAL DIOLS;

CHEMICAL BONDS; KETONES; MANGANESE COMPOUNDS; STEREOCHEMISTRY; STEREOSELECTIVITY;

MANGANESE;

BIS(CYCLOPENTADIENYL)TITANIUM(III) CHLORIDE; KETONE DERIVATIVE; LEWIS ACID; MANGANESE; REAGENT; TITANOCENE; UNCLASSIFIED DRUG; ZINC;

ARTICLE; CHEMICAL BOND; CHEMICAL INTERACTION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONFORMATIONAL TRANSITION; CROSS COUPLING REACTION; CYCLIZATION; PINACOL REARRANGEMENT; PROTON NUCLEAR MAGNETIC RESONANCE; RING OPENING; STEREOCHEMISTRY; SYNTHESIS;

EID: 66449136019     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9005238     Document Type: Article

References (64)

1. For pertinent reviews, see: (a) Gansäuer, A.; Bluhm, H. Chem. Rev. 2000, 100, 2771-2788.
2. (b) Gansäuer, A.; Pierobon, M. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, Germany, 2001; Vol. 2, pp 207-220.
3. (c) Gansäuer, A.; Narayan, S. Adv. Synth. Catal. 2002, 344, 465-475.
4. (d) Gansäuer, A.; Lauterbach, T.; Narayan, S. Angew. Chem., Int. Ed. 2003, 42, 5556-5573.
5. (e) Cuerva, J. M.; Justicia, J.; Oller-López, J. L.; Oltra, J. E. Top. Curr. Chem. 2006, 264, 63-91.
6. For pioneering reports on epoxide opening promoted by Nugent's reagent, see:(a) RajanBabu, T. V.; Nugent, W. A. J. Am. Chem. Soc. 1994, 116, 986-997, and references cited therein.
7. (b) Gansäuer, A.; Bluhm, H.; Pierobon, M. J. Am. Chem. Soc. 1998, 120, 12849-12859.
8. (c) Barrero, A. F.; Rosales, A.; Cuerva, J. M.; Oltra, J. E. Org. Lett. 2003, 5, 1935-1938.
9. (a) Justicia, J.; Rosales, A.; Buñuel, E.; Oller-López, J. L.; Valdivia, M.; Haïdour, A.; Oltra, J. E.; Barrero, A. F.; Cárdenas, D. J; Cuerva, J. M. Chem.sEur. J. 2004, 10, 1778-1788.
10. (b) Justicia, J. E; Oltra, J. M; Cuerva, J. Org. Chem. 2004, 69, 5803-5806.
11. (c) Justicia, J.; Oltra, J. E.; Cuerva, J. M. J. Org. Chem. 2005, 70, 8265-8272.
12. (d) Justicia, J.; Oller-López, J. L.; Campaña, A. G.; Oltra, J. E.; Cuerva, J. M.; Buñuel, E.; Cárdenas, D. J. J. Am. Chem. Soc. 2005, 127, 14911-14921.
13. Estévez, R. E.; Oller-López, J. L.; Robles, R.; Melgarejo, C. R.; Gansäuer, A.; Cuerva, J. M.; Oltra, J. E. Org. Lett. 2006, 8, 5433-5436.
14. Cuerva, J. M.; Campaña, A. G.; Justicia, J.; Rosales, A.; Oller-López, J. L.; Robles, R.; Cárdenas, D.; Buñuel, E.; Oltra, J. E. Angew. Chem., Int. Ed. 2006, 45, 5522-5526.
15. Campaña, A. G.; Estévez, R. E.; Fuentes, N.; Robles, R.; Cuerva, J. M.; Buñuel, E.; Cárdenas, D.; Oltra, J. E. Org. Lett. 2007, 9, 2195-2198.
16. Campaña, A. G.; Bazdi, B.; Fuentes, N.; Robles, R.; Cuerva, J. M.; Oltra, J. E.; Porcel, S.; Echavarren, A. M. Angew. Chem., Int. Ed. 2008, 47, 7515-7519.
17. (a) Rosales, A.; Oller-López, J. L.; Justicia, J.; Gansäuer, A.; Oltra, J. E.; Cuerva, J. M. Chem. Commun. 2004, 2628-2629.
18. (b) Estévez, R. E.; Justicia, J.; Bazdi, B.; Fuentes, N.; Paradas, M.; Choquesillo-Lazarte, D.; García-Ruiz, J. M.; Robles, R.; Gansäuer, A.; Cuerva, J. M.; Oltra, J. E. Chem.sEur. J. 2009, 15 , 2774-2791.
19. (a) Handa, Y.; Inanaga, J. Tetrahedron Lett. 1987, 28, 5717-5718.
20. (b) Gansäuer, A. Chem. Commun. 1997, 457-458.
21. (c) Gansäuer, A.; Bauer, D. J. Org. Chem. 1998, 63, 2070-2071.
22. (d) Gansäuer, A.; Bauer, D. Eur. J. Org. Chem. 1998, 2673-2676.
23. (e) Hirao, T.; Hatano, B.; Asahara, M.; Muguruma, Y.; Ogawa, A. Tetrahedron Lett. 1998, 39, 5247-5248.
24. (f) Dunlap, M. S.; Nicholas, K. M. J. Organomet. Chem. 2001, 630, 125-131.
25. Barden, M. C.; Schwartz, J. J. Am. Chem. Soc. 1996, 118, 5484-5485.
26. Nugent's reagent generated in situ by stirring commercial Cp2TiCl2 with Zn or Mn dust in THF exists as an equilibrium mixture of the monomer Cp2TiCl and the dinuclear species (Cp2TiCl)2; see: (a) Enemærke, R. J.; Larsen, J.; Skrydstrup, T.; Daasbjerg, K. J. Am. Chem. Soc. 2004, 126, 7853-7864.
27. (b) Daasbjerg, K.; Svith, H.; Grimme, S.; Gerenkamp, M.; Mück-Lichtenfeld, C.; Gansäuer, A.; Barchuck, A.; Keller, F. Angew. Chem., Int. Ed. 2006, 45, 2041-2044.
28. (c) Gansäuer, A.; Barchuk, A.; Keller, F.; Schmitt, M.; Grimme, S.; Gerenkamp, M.; Mück-Lichtenfeld, C.; Daasbjerg, K.; Svith, H. J. Am. Chem. Soc. 2007, 129, 1359-1371.
29. Oller-López, J. L.; Campaña, A. G.; Cuerva, J. M.; Oltra, J. E. Synthesis 2005, 2619-2622.
30. For more details, including experimental ones, see the Supporting Information.
31. For a helpful discussion about the stereoselectivity in TiIII-mediated pinacolizations, see: Enemærke, R. J.; Larsen, J.; Hjollund, G. H.; Skrydstrup, T.; Daasbjerg, K. Organometallics 2005, 24, 1252-1262.
32. For a recent review of stereoselective pinacol coupling reactions, see: Chatterjee, A.; Joshi, N. N. Tetrahedron 2006, 62, 12137-12158.
33. (a) Nishiyama, Y.; Shinomiya, E.; Kimura, S.; Itoh, K.; Sonoda, N. Tetrahedron Lett. 1998, 39, 3705-3708.
34. (b) Ogawa, A.; Takeuchi, H.; Hirao, T. Tetrahedron Lett. 1999, 40, 7113-7114.
35. (c) Arai, S.; Sudo, Y.; Nishida, A. Chem. Pharm. Bull. 2004, 52, 287-288.
36. (d) Aspinall, H. C.; Greeve, N.; Valla, C. Org. Lett. 2005, 7, 1919-1922.
37. Cyclic voltammograms of different titanocene(III) complexes determined in THF indicated potential values considerably less negative than that of SmI2, one of the most commonly used single-electron-transfer reagents; see: Enemærke, R. J.; Daasbjerg, K.; Skrydstrup, T. Chem. Commun. 1999, 343-344.
38. The described E0 value for Mn2+/Mn is-1.18 vs hydrogen electrode: Handbook of Chemistry and Physics, 85th ed.; Lide, D. R., Ed.; CRC Press: Boca Raton, 2004; pp 8-25-8-26.
39. (a) Douch, J.; Mousset, G. Can. J. Chem. 1987, 65, 549-556.
40. (b) Fournier, F.; Fournier, M. Can. J. Chem. 1986, 64, 881-890.
41. Tanaka, K.; Kishigami, S.; Toda, F. J. Org. Chem. 1990, 55, 2981-2983.
42. Together with the nucleophilic-coupling mechanism depicted in Scheme 2, the conventional bimolecular radical-radical pinacol coupling mechanism9 possibly coexists, but especially under the conditions with substoichiometric proportions of titanium, the former probably prevails.
43. Sato, F.; Iida, K.; Ijima, S.; Moriya, H.; Sato, M. Chem. Commun. 1981, 1140-1141.
44. Aliphatic ketones were inert under these reaction conditions.
45. Yamamoto, Y.; Hattori, R.; Miwa, T.; Nakagai, Y.-i.; Kubota, T.; Yamamoto, C.; Okamoto, Y.; Itoh, K J. Org. Chem. 2001, 66, 3865-3870.
46. (a) Fujiwara, T.; Tsuruta, Y.; Arizono, K.; Takeda, T. Synlett 1997, 962-964.
47. (b) Balskus, E. P.; Méndez-Andino, J.; Arbit, R. M.; Paquette, L. A. J. Org. Chem. 2001, 66, 6695-6704.
48. For a recent review, see: Kagan, H. B. Tetrahedron 2003, 59, 10351-10372.
49. For other regenerating agents, see: (a) Reference 1b.
50. (b) Gansäuer, A.; Bluhm, H.; Rinker, B.; Narayan, S.; Schick, M.; Lauterbach, T.; Pierobon, M. Chem.sEur. J. 2003, 9, 531-542.
51. (c) Gansäuer, A.; Lauterbach, T.; Narayan, S. Angew. Chem., Int. Ed. 2003, 42, 5556-5573.
52. (d) Fuse, S.; Hanochi, M.; Doi, T.; Takahashi, T. Tetrahedron Lett. 2004, 45, 1961-1963.
53. For a related titanium(III)-based system, see: Hirao, T.; Hatano, B.; Asahara, M.; Muguruma, Y.; Ogawa, A. Tetrahedron Lett. 1998, 39, 5247-5248.
54. (a) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729-1734.
55. (b) Seebach, D.; Oie, H. A.; Daum, H. Chem. Ber. 1977, 110, 2316-2333.
56. Goossen, L. J.; Ghosh, K. Eur. J. Org. Chem. 2002, 3254-3267.
57. Li, L.-Z.; Xiao, B.; Guo, Q.-Z.; Xue, S. Tetrahedron 2006, 62, 7762-7771.
58. Balskus, E. P.; Méndez-Andino, J.; Arbit, R. M.; Paquette, L. A. J. Org. Chem. 2001, 66, 6695-6704.
59. Balu, N.; Nayak, S. K.; Banerji, A. J. Am. Chem. Soc. 1996, 118, 5932-5937.
60. Pons, J.-M.; Santelli, M. J. Org. Chem. 1989, 54, 877-884.
61. Kobayashi, S.; Endo, M.; Nagayama, S. J. Am. Chem. Soc. 1999, 121, 11229-11230.
62. Kise, N.; Shiozawa, Y.; Ueda, N. Tetrahedron 2007, 63, 3415-5426.
63. Garnier, J. M.; Robin, S.; Rousseau, G. Eur. J. Org. Chem. 2007, 3281-3291.
64. Fang, J.-M.; Hong, B.-C.; Liao, L.-F. J. Org. Chem. 1987, 52, 855-861.