Titanium/palladium-mediated regioselective propargylation of ketones using propargylic carbonates as pronucleophiles

Advanced Synthesis and Catalysis

Volumn 353, Issue 1, 2011, Pages 73-78

  Millán, Alba ^a   De Cienfuegos, Luis Álvarez ^a   Martín Lasanta, Ana ^a   Campaña, Araceli G ^a   Cuerva, Juan M ^a  

^a UNIVERSITY OF GRANADA   (Spain)

Author keywords

homogeneous catalysis; propargylation; radical reactions; synthetic methods; titanium

Indexed keywords

EID: 79251518284     PISSN: 16154150     EISSN: 16154169     Source Type: Journal    
DOI: 10.1002/adsc.201000655     Document Type: Article

References (56)

1. For recent reviews, see S. T. Diver, A. J. Giessert, Chem. Rev. 2004, 104, 1317-1382
2. E. Jiménez-Nãñez, A. M. Echavarren, Chem. Rev. 2008, 108, 3326-3350.
3. For recent syntheses, see: J. D. Trenkle, T. F. Jamison, Angew. Chem. 2009, 121, 5470-5472
4. Angew. Chem. Int. Ed. 2009, 48, 5366-5368
5. K. Molawi, N. Delpont, A. M. Echavarren, Angew. Chem. Int. Ed. 2010, 49, 3517-3519.
6. For recent references, see: H. Yamamoto, in: Comprehensive Organic Synthesis, (Eds.:, B. M. Trost, I. Fleming,), Pergamon Press: Oxford, 1991, Vol. 2, pp. 81-98. For recent references, see
7. D. R. Fandrick, K. R. Fandrick, J. T. Reeves, Z. Tan, C. S. Johnson, H. Lee, J. J. Song, N. K. Yee, C. H. Senayake, Org. Lett. 2010, 12, 88-91
8. S.-L. Shi, L.-X. Xu, K. Oisaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2010, 132, 6638-6639
9. D. R. Fandrick, K. R. Fandrick, J. T. Reeves, Z. Tan, W. Tang, A. G. Capacci, S. Rodriguez, J. J. Song, H. Lee, N. K. Yee, C. H. Senayake, J. Am. Chem. Soc. 2010, 132, 7600-7601.
10. A. Fürstner, Chem. Rev. 1999, 99, 991-1046
11. P. Place, C. Verniere, J. Gore, Tetrahedron 1981, 37, 1359-1367
12. K. Namba, Y. Kishi, Org. Lett. 2004, 6, 5031-5033
13. M. Inoue, M. Nakada, Org. Lett. 2004, 6, 2977-2980.
14. P. Girard, J. L. Namy, H. B. Kagan, J. Am. Chem. Soc. 1980, 102, 2693-2698.
15. T. Imamoto, T. Kusumoto, Y. Tawarayama, Y. Sugiura, T. Mita, Y. Hatanaka, M. Yokohama, J. Org. Chem. 1984, 49, 3904-3912.
16. R. Baker, M. A. Brimble, Tetrahedron Lett. 1986, 27, 3311-3314.
17. C. Chen, D. J. Crich, J. Chem. Soc. Chem. Commun. 1991, 1289-1290
18. L. W. Bieber, M. F. da Silva, R. C. da Costa, L. O. S. Silva, Tetrahedron Lett. 1998, 39, 3655-3658.
19. B. Alcaide, P. Almendros, C. Aragoncillo, R. Rodríguez-Acebes, J. Org. Chem. 2001, 66, 5208-5216.
20. M. Banarjee, S. Roy, Chem. Commun. 2003, 534-535.
21. S. Singh, S. Kumar, S. S. Chimni, Tetrahedron: Asymmetry 2002, 13, 2679-2687
22. T.-P. Loh, M.-J. Lin, K.-L. Tan, Tetrahedron Lett. 2003, 44, 507-509
23. W. Miao, W. Lu, T. H. Chan, J. Am. Chem. Soc. 2003, 125, 2412-2413
24. J. Park, S. Kim, P. H. Lee, Org. Lett. 2008, 10, 5067-5070.
25. J. Justicia, I. Sancho-Sanz, E. Ãlvarez-Manzaneda, J. E. Oltra, J. M. Cuerva, Adv. Synth. Catal. 2009, 351, 2295-2300.
26. 2, or samarium(II) complexes, have been described. Nevertheless, these protocols have some limitations derived from the reaction conditions or the reactivity of the corresponding organometallic species, as well as they provide mixtures of regioisomers
27. Y. Tamaru, S. Goto, A. Tanaka, M. Shimizu, M. Kimura, Angew. Chem. 1996, 108, 962-963
28. Angew. Chem. Int. Ed. Engl. 1996, 35, 878-880
29. T. Tabuchi, J. Inanaga, M. Yamaguchi, Chem. Lett. 1987, 2275-2278
30. J. M. Aurrecoechea, R. Fañanas, M. Arrate, J. M. Gorgojo, N. Aurrekoetxea, J. Org. Chem. 1999, 64, 1893-1901
31. Y. Makioka, K. Koyama, T. Nishiyama, K. Takaki, Y. Taniguchi, Y. Fujiwara, Tetrahedron Lett. 1995, 36, 6283-6286.
32. Methods based on Ti(II) have a better profile but they are limited by the use of (over)stoichiometric amounts of titanium(II) complexes
33. T. Nakawawa, A. Kasatkin, F. Sato, Tetrahedron Lett. 1995, 36, 3207-3210
34. S. Okamoto, D. K. An, F. Sato, Tetrahedron Lett. 1998, 39, 4551-4554
35. S. Okamoto, D. K. An, F. Sato, Tetrahedron Lett. 1998, 39, 4861-4864
36. T. Hanazawa, S. Okamoto, F. Sato, Org. Lett. 2000, 2, 2369-2371
37. F. Yang, G. Zhao, Y. Ding, Tetrahedron Lett. 2001, 42, 2839-2841
38. C. Delas, S. Okamoto, F. Sato, Tetrahedron Lett. 2002, 43, 4373-4375
39. F. Yang, G. Zhao, Y. Ding, Z. Zhao, Y. Zheng, Tetrahedron Lett. 2002, 43, 1289-1293
40. Y. Yatsumonji, T. Sugita, A. Tsubouchi, T. Takeda, Org. Lett. 2010, 12, 1968-1971.
41. 2TiCl to transfer a Cp group by Grignard-type reactions:, R. Horacio, A. L. Dieguez, D. Victoriano, J. F. Arteaga, J. A. Dobado, M. M. Herrador, J. F. Quílez del Moral, A. F. Barrero, J. Am. Chem. Soc. 2010, 132, 254-259.
42. A. G. Campaña, B. Bazdi, N. Fuentes, R. Robles, J. M. Cuerva, J. E. Oltra, S. Porcel, A. M. Echavarren, Angew. Chem. 2008, 120, 7625-7629
43. Angew. Chem. Int. Ed. 2008, 47, 7515-7519.
44. 2TiCl.
45. Manganese is usually used in excess (800 mol%) but it can be filtered and reused in subsequent experiments.
46. 2TiCl and Pd catalyst loadings can be smaller but in some cases incomplete conversions are obtained. The reported loadings have been optimized for complete conversions in all the experiments.
47. 2,4,6-Collidine can be recovered at the end of the reaction by a simple acid-base extraction.
48. The stereochemistry was assigned by chemical correlation with the corresponding alkene derivative:, D. Seebach, L. Widler, Helv. Chim. Acta 1982, 65, 1972-1981.
49. M. Ishiguro, N. Ikeda, H. Yamamoto, J. Org. Chem. 1982, 47, 2225-2227.
50. 2TiCl:, M. Paradas, A. G. Campaña, R. E.; Estévez, L. Ãlvarez de Cienfuegos, T. Jiménez, R. Robles, J. M. Cuerva, J. E. Oltra, J. Org. Chem. 2009, 74, 3616-3619.
51. Nevertheless, alternative mechanisms based on a direct addition of propargylic radicals to the carbonyl compound in the presence of titanocene(III) cannot be ruled out
52. A. Fernández-Mateos, S. Encinas Madrazo, P. Herrero Teijõn, R. Rubio González, J. Org. Chem. 2009, 74, 3913-3918. This mechanism can also explain the excellent regiochemistry taking into account that in substituted propargylic radicals the alkyne form prevails
53. C. L. Parker, A. L. Cooksy, J. Phys. Chem. A 1999, 103, 2160. For a related mechanism using the Nozaki-Hiyama-Kishi reaction see
54. M. Bandini, P. G. Cozzi, A. Umani-Ronchi, Polyhedron 2000, 19, 537-539.
55. 2 has been described:, R. S. P. Coutts, P. C. Wailes, R. L. Martin, J. Organomet. Chem. 1973, 47, 375-382.
56. 2TiCl is an air-sensitive compound, oxygen must be removed from the solution. Therefore, argon or nitrogen gas must be bubbled through the solvent (THF) during 10 min prior to use.