Titanocene-Catalyzed Reduction of Lactones to Lactols

Journal of Organic Chemistry

Volumn 62, Issue 24, 1997, Pages 8522-8528

  Verdaguer, Xavier ^a,b   Hansen, Marcus C ^a   Berk, Scott C ^a,c   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

^b UNIVERSITY OF BARCELONA   (Spain)

^c MERCK RESEARCH LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000658315     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971560s     Document Type: Article

References (60)

1. Rylander, P. N. Hydrogenation Methods; Academic Press: New York, 1985.
2. Chaloner, P. A.; Esteruelas, M. A.; Jou, F.; Oro, L. A. Homogeneous Hydrogenation; Kluwer Academic: Boston, 1994.
3. Ojima, I. In The Chemistry of Organic Silicon Compounds, Part 2; Wiley: New York, 1989; pp 1479-1526.
4. (a) Kanazawa, R.; Tokoroyama, T. Synthesis 1976, 526.
5. (b) Cha, J. S.; Min, S. J.; Lee, J. C.; Lee, H. S.; Lee, S. E. Org. Prep. Proced. Int. 1992, 24, 335.
6. (a) Winterfeldt, E. Synthesis 1975, 617.
7. (b) Takacs, J. M.; Helle, M. A.; Seely, F. L. Tetrahedron Lett. 1986, 27, 1257.
8. (a) Berk, S. C.; Kreutzer, K. A.; Buchwald, S. L. J. Am. Chem. Soc. 1991, 113, 3, 5093.
9. (b) Barr, K. J.; Berk, S. C.; Buchwald, S. L. J. Org. Chem. 1994, 59, 4323.
10. (a) Verdaguer, X.; Lange, U. E. W.; Reding, M. T.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 6784.
11. (b) Broene, R. D.; Buchwald, S. L. J. Am. Chem. Soc. 1993, 115, 12569.
12. (c) Lee, N. E.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 5985.
13. Verdaguer, X.; Berk, S. C.; Buchwald, S. L. J. Am. Chem. Soc. 1995, 117, 12641.
14. Berk, S. C. Ph.D. Thesis, Massachusetts Institute of Technology, 1994.
15. Brintzinger, H. H. J. Am. Chem. Soc. 1967, 89, 6871.
16. Martin, H. A.; Jellinek, F. J. Organomet. Chem. 1968, 12, 149.
17. (a) Aitken, C. T.; Harrod, J. F.; Samuel, E. J. Am. Chem. Soc. 1986, 108, 4059.
18. (b) Harrod, J. F.; Mu, Y.; Samuel, E. Can. J. Chem. 1992, 70, 2980.
19. Bourg, S.; Corriu, R. J. P.; Enders, M.; Moreau, J. J. E. Organometallics 1995, 14, 564.
20. Andra, K. J. Organomet. Chem. 1968, 11, 567.
21. 15% TBAF by weight.
22. Druce, P. M.; Kingston, B. M.; Lappert, M. F.; Spalding, T. R.; Srivastava, R. C. J. Chem. Soc. A 1969, 2106.
23. (a) Spaltenstein, E.; Palma, P.; Kreutzer, K. A.; Willoughby, C. A.; Davis, W. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 10308.
24. (b) Xin, S.; Harrod, J. F.; Samuel, E. J. Am. Chem. Soc. 1994, 116, 11562.
25. (c) de Wolf, J. M.; Meetsma, A.; Teuben, J. H. Organometallics 1995, 14, 5466.
26. 2 catalyze the redistribution of polymethylhydrosiloxanes; see: Laine, R. L.; Rahn, J. A.; Youngdahl, K. A.; Babonneau, F.; Hoppe, M. L.; Zhang, Z. F.; Harrod, J. F. Chem. Mater. 1990, 2, 464. Xin, S., Aitken, C.; Harrod, J. F.; Mu, Y.; Samuel, E. Can. J. Chem. 1990, 68, 471.
27. 2 catalyze the redistribution of polymethylhydrosiloxanes; see: Laine, R. L.; Rahn, J. A.; Youngdahl, K. A.; Babonneau, F.; Hoppe, M. L.; Zhang, Z. F.; Harrod, J. F. Chem. Mater. 1990, 2, 464. Xin, S., Aitken, C.; Harrod, J. F.; Mu, Y.; Samuel, E. Can. J. Chem. 1990, 68, 471.
28. Verdaguer, X.; Buchwald, S. L. Unpublished results.
29. A dimeric titanocene(III) fluoride has been described; see: Coutts, R. S. P.; Wailes, P. C.; Martin, R. L. J. Organomet. Chem. 1973, 47, 375.
30. Attempts to use less than 5 equiv of PMHS resulted in incomplete reduction. We believe attachment of a lactol to the siloxane polymer hinders the vicinal Si-H positions, thereby reducing the effective number of hydride equivalents.
31. Woo, H-G.; Tilley, T. D. J. Am. Chem. Soc. 1989, 111, 3757.
32. (a) Kesti, M. R.; Waymouth, R. M. Organometallics 1992, 11, 1095.
33. (b) Harrod, J. F.; Yun, S. S. Organometallics 1987, 6, 1381.
34. (a) Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 8952.
35. (b) Colomer, E.; Corriu, R. J. Organomet. Chem. 1974, 82, 367.
36. Dehalogenation has not been a difficulty in other hydrosilylation reactions we have investigated. See ref 6 and: Carter, M. B.; Schiøtt, B.; Gutiérrez, A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 11667.
37. Hurd, C. D.; Saunders, W. H., Jr. J. Am. Chem. Soc. 1952, 74, 5324.
38. (a) Furin, G. G.; Vyazakina, O. A.; Gostevsky, B. A.; Vyazankin, N. S. Tetrahedron 1988, 44, 2675.
39. (b) Chuit, C.; Corriu, R. J. P.; Reye, C.; Young, J. C. Chem. Rev. (Washington, D.C.) 1993, 93, 1371.
40. Fujita, M.; Hiyama, T. J. Org. Chem. 1988, 53, 5405.
41. Chem. Eng. News 1996; Sept. 16, 42.
42. Shiihara, I.; Kawai, W.; Ichihashi, T. J. Polym. Sci. 1962, 57, 837.
43. For reduction of a lactone see: Boyer, J.; Corriu, R. J. P.; Perz, R.; Poirier, M.; Reye, C. Synthesis 1981, 558. But, lactones were stable to the conditions used in: Chuitt, C.; Corriu, R. J. P.; Perz, R.; Reyé, C. Synthesis 1982, 981.
44. For reduction of a lactone see: Boyer, J.; Corriu, R. J. P.; Perz, R.; Poirier, M.; Reye, C. Synthesis 1981, 558. But, lactones were stable to the conditions used in: Chuitt, C.; Corriu, R. J. P.; Perz, R.; Reyé, C. Synthesis 1982, 981.
45. Saucy, G.; Borer, R. Helv. Chim. Acta 1971, 54, 2121.
46. Dana, G.; Figadère, B.; Touboul, E. Tetrahedron Lett. 1985, 26, 5683.
47. Bates, R. W.; Díez-Martín, D.; Kerr, W. J.; Knight, J. G.; Ley, S. V.; Sakellaridis, A. Tetrahedron 1990, 46, 4063.
48. Yates, P.; Macas, T. S. Can. J. Chem. 1988, 66, 1.
49. Marner, F.-J.; Jaenicke, L. Chem. Ber. 1975, 108, 2202.
50. Bloomfield, J. J.; Lee, S. L. J. Org. Chem. 1967, 32, 3919.
51. Bailey, D. M.; Johnson, R. E. J. Org. Chem. 1970, 35, 3574.
52. Lhoste, P.; Moreau, M.; Dreux, J. Tetrahedron 1984, 40, 1551.
53. (a) Fouda, H. G.; Lukaszewicz, J.; Clark, D. A.; Hulin, B. Xenobiotica 1991, 21, 925.
54. (b) Davies, S. G.; Pyatt, D.; Thomson, C. J. Organomet. Chem. 1990, 387, 381.
55. Dale, J.; Morgenlie, S. Acta Chem. Scand. 1970, 24, 2408.
56. Zvilichovsky, G.; Fotadar, U. Org. Prep. Proced. Int. 1974, 6, 5.
57. Freeman, F.; Robarge, K. D. Carbohydr. Res. 1985, 137, 89.
58. Marquez, V. E.; Lim, M.-I.; Khan, M. S.; Kaskar, B. Nucleic Acid Chem. 1991, 4, 27.
59. Ohloff, G.; Vial, C.; Demole, E.; Enggist, P.; Giersch, W.; Jégou, E.; Caruso, A. J.; Polonsky, J.; Lederer, E. Helv. Chim. Acta 1986, 69, 163.
60. Gutman, A. L.; Zuobi, K.; Bravdo, T. J. Org. Chem. 1990, 55, 3546.