Highly Stereoselective Synthesis of syn-1,3-Diols through a Sequential Titanium-Mediated Aldol Reaction and LiBH4 Reduction

European Journal of Organic Chemistry

Volumn , Issue 16, 2010, Pages 3146-3151

  Esteve, Judit ^a   Matas, Sònia ^a   Pellicena, Miquel ^a   Velasco, Javier ^a   Romea, Pedro ^a   Urpí, Fèlix ^a   Font Bardia, Mercè ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

Aldol reactions; Chirality; Ketones; Reduction; Sequential transformation; Stereoselective synthesis

Indexed keywords

EID: 77952646513     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.201000293     Document Type: Article

References (53)

1. a) B. M. Trost, Science 1991, 254, 1471-1477;
2. b) B. M. Trost, Angew. Chem. Int. Ed. Engl. 1995, 34, 259-281;
3. (c) P. A. Wender, M. P. Croatt, B. Witulski, Tetrahedron 2006, 62, 7505-7511;
4. (d) N. Z. Burns, P. S. Baran, R. W. Hoffmann, Angew. Chem. Int. Ed. 2009, 48, 2854-2867.
5. a) L. F. Tietze, U. Beifuss, Angew. Chem. Int. Ed. Engl. 1993, 32, 131-163;
6. b) L. F. Tietze, Chem. Rev. 1996, 96, 115-136;
7. (c) J.-C. Wasilke, S. J. Obrey, R. T. Baker, G. C. Bazan, Chem. Rev. 2005, 105, 1001-1020.
8. [2c|).
9. K. C. Nicolaou, D. J. Edmonds, P. G. Bulger, Angew. Chem. Int. Ed. 2006, 45, 7134-7186.
10. For a review on the stereoselective synthesis of 1,3-diols, see: S. E. Bode, M. Wolberg, M. Müller, Synthesis 2006, 557-588.
11. For a recent example on a sequential aldol transformation leading to 1,3-diols, see: M. B. Boxer, M. Akakura, H. Yamamoto, J. Am. Chem. Soc. 2008, 130, 1580-1582.
12. a) K. Narasaka, F.-C. Pai, Tetrahedron 1984, 40, 2233-2238;
13. b) K.-M. Chen, G. E. Hardtmann, K. Prasad, O. Repic, M. J. Shapiro, Tetrahedron Lett. 1987, 28, 155-158.
14. a) J. Paterson, M. V. Perkins, Tetrahedron Lett. 1992, 33, 801-804;
15. b) I. Paterson, M. V. Perkins, Tetrahedron 1996, 52, 1811-1834.
16. For parallel, processes involving chiral boron. Lewis acids, see: a) C. Bonini, R. Racioppi, G. Righi, L. Rossi, Tetrahedron: Asymmetry 1994, 5, 173-176;
17. b) Y. Kaneko, T. Matsuo, S.-i. Kiyooka, Tetrahedron Lett. 1997, 38, 4107-4110.
18. Otherwise, anti-1,3-diols can be prepared through the Tishchenko aldol procedure, a sequential transformation based on an aldol reaction followed by the intramolecular hydride delivery. For a review and a recent example, see: a) J. Mlynarski, Eur. J. Org. Chem. 2006, 4779-4786;
19. b) K. Rohr, R. Herre, R. Malirwald, J. Org. Chem. 2009, 74, 3744-3749.
20. For examples of this sequential transformation in total synthesis, see: a) I. Paterson, M. D. McLeod, Tetrahedron Lett. 1997, 38, 4183-4186;
21. b) K. C. Nicolaou, F. Murphy, S. Barluenga, T. Ohshima, H. Wei, J. Xu, D. L. F. Gray, O. Baudoin, J. Am. Chem. Soc. 2000, 122, 3830-3838;
22. (c) M. Carda, S. Rodriguez, B. Segovia, J. A. Marco, J. Org. Chem. 2002, 67, 6560-6563;
23. (d) S. A. Burova, F. E. McDonald, J. Am. Chem. Soc., 2004, 126, 2495-2500;
24. e) I. Paterson, I. Lyothier, J. Org. Chem. 2005, 70, 5494-5507;
25. f) I. Paterson, K. Ashton, R. Britton, G. Cecere, G. Chouraqui, G. J. Florence, H. Knust, J. Stafford, Chem. Asian J. 2008, 3, 367-387.
26. 2/NaOH triggered the partial migration of the TBS protecting group. Although this drawback was sorted out by using milder oxidative conditions, the purification of the resultant 1,3-diols was hampered by the presence of non-identified impurities. See, M. Galobardes, M. Mena, P. Romea, F. Urpí, J. Vilarrasa, Tetrahedron Lett. 2002, 43, 6145-6148.
27. For an Al-based procedure, see: S.-i. Kiyooka, H. Kuroda, Y. Shimasaki, Tetrahedron Lett. 1986, 27, 3009-3012.
28. For a Zn-based procedure, see: T. Nakata, Y. Tani, M. Hatozaki, T. Oishi, Chem. Pharm. Bull. 1984, 32, 1411-1415.
29. a) C. R. Sarko, I. C. Guch, M. DiMare, J. Org. Chem. 1994, 59, 705-706;
30. b) C. R. Sarko, S. E. Collibee, A. L. Knorr, M. DiMare, J. Org. Chem. 1996, 61, 868-873.
31. a) G. Bartoli, M. Bosco, E. Marcantoni, M. Massaccesi, S. Rinaldi, L. Sambri, Eur. J. Org. Chem. 2001, 4679-4684;
32. b) G. Bartoli, M. Bosco, M. C. Bellucci, R. Dalpozzo, E. Marcantoni, L. Sambri, Org. Lett. 2000, 2, 45-47;
33. (c) G. Bartoli, M. C. Bellucci, M. Bosco, R. Dalpozzo, E. Marcantoni, L. Sambri, Chem. Eur. J. 2000, 6, 2590-2598.
34. a) S. Figueras, R. Martin, P. Romea, F. Urpi, J. Vilarrasa, Tetrahedron Lett. 1997, 38, 1637-1640;
35. b) I. Larrosa, P. Romea, F. Urpi, Org. Lett. 2006, 8, 527-530;
36. (c) J. Nebot, S. Figueras, P. Romea, F. Urpí, Y. Ji, Tetrahedron 2006, 62, 11090-11099;
37. (d) J. Nebot, P. Romea, F. Urpi, J. Org. Chem. 2009, 74, 7518-7521;
38. e) A. Lorente, M. Pellicena, P. Romea, F. Urpi, Tetrahedron Lett. 2010, 51, 942-945.
39. [12].
40. 4 to afford the racemic 1,2-syn-1,3-syn diol in 62% yield and ds = 9.1%. R. Mahrwald, B. Ziemer, Tetrahedron 1999, 55, 14005-14012.
41. a) R. Martín, O. Pascual, P. Romea, R. Rovira, F. Urpí, J. Vilarrasa, Tetrahedron Lett. 1997, 38, 1633-1636;
42. b) M. Perrero, M. Galobardes, R. Martín, T. Montes, P. Romea, R. Rovira, F. Urpí, J. Vilarrasa, Synthesis 2000, 1608-1614.
43. [17d]
44. It is worth mentioning that the aldol reaction from bromo ketone 2 usually affords slightly lower yields than the related process from ketone 1.
45. Modern Aldol Reactions (Ed.: R. Mahrwald), Wiley-VCH, Weinlieim, 2004.
46. [17e]
47. We speculate that the known, ability of TBS protecting group to migrate can be enhanced in this occasion because C3-hydroxy is sterically more hindered than C4-hydroxy.
48. For the proof of the stereochemistry, see Supporting Information.
49. CCDC-766003 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallograpliic Data Center via www.ccdc.cam.ac.uk/data-request/cif.
50. For seminal contributions on stereoselective aldol reactions based on chiral α-hydroxy ketones, see: a) S. Masamune, W. Clioy, F. A. J. Kerdesky, B. Imperiali, J. Am. Chem. Soc. 1981, 103, 1566-1568;
51. b) N. A. Van Draanen, S. Arseniyadis, M. T. Crimmins, C. H. Heathcock, J. Org. Chem. 1991, 56, 2499-2506;
52. (c) I. Paterson, D. J. Wallace, S. M. Velazquez, Tetrahedron Lett. 1994, 33, 9083-9086.
53. A small amount of diastereomerically pure triol 6a was isolated and was used for a better identification.