Enantioselective construction of quaternary stereogenic centers from tertiary boronic esters: Methodology and applications

Angewandte Chemie - International Edition

Volumn 50, Issue 16, 2011, Pages 3760-3763

  Sonawane, Ravindra P ^a   Jheengut, Vishal ^a   Rabalakos, Constantinos ^a   Larouche Gauthier, Robin ^a   Scott, Helen K ^a   Aggarwal, Varinder K ^a  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

Author keywords

Borates; Chirality; Natural products; Olefination; Stereogenic centers

Indexed keywords

BORATES; BORONIC ESTERS; ENANTIOSELECTIVE CONSTRUCTION; HIGH ENANTIOSELECTIVITY; NATURAL PRODUCT SYNTHESIS; NATURAL PRODUCTS; OLEFINATION; STEREOGENIC CENTERS;

CHIRALITY; ENANTIOMERS; ENANTIOSELECTIVITY; ESTERIFICATION; FUNCTIONAL GROUPS; STEREOCHEMISTRY;

ESTERS;

EID: 79953714571     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201008067     Document Type: Article

References (61)

1. For reviews see: a) C. Hawner, A. Alexakis, Chem. Commun. 2010, 46, 7295-7306;
2. b) M. Bella, T. Gasperi, Synthesis 2009, 1583-1614;
3. c) O. Riant, J. Hannedouche, Org. Biomol. Chem. 2007, 5, 873-888;
4. d) I. Marek, G. Sklute, Chem. Commun. 2007, 1683-1691;
5. e) P. G. Cozzi, R. Hilgraf, N. Zimmermann, Eur. J. Org. Chem. 2007, 5969-5994;
6. f) B. M. Trost, C. Jiang, Synthesis 2006, 369-396;
7. g) J. Christoffers, A. Baro, Adv. Synth. Catal. 2005, 347, 1473-1482;
8. h) C. J. Douglas, L. E. Overman, Proc. Natl. Acad. Sci. USA 2004, 101, 5363-5367;
9. i) J. Christoffers, A. Baro, Angew. Chem. 2003, 115, 1726-1728;
10. Angew. Chem. Int. Ed. 2003, 42, 1688-1690;
11. j) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732;
12. Angew. Chem. Int. Ed. 2001, 40, 4591-4597;
13. k) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415;
14. Angew. Chem. Int. Ed. 1998, 37, 388-401;
15. l) K. Fuji, Chem. Rev. 1993, 93, 2037-2066.
16. a) J. L. Stymiest, V. Bagutski, R. French, V. K. Aggarwal, Nature 2008, 456, 778-782;
17. b) V. Bagutski, R. M. French, V. K. Aggarwal, Angew. Chem. 2010, 122, 5268-5271;
18. Angew. Chem. Int. Ed. 2010, 49, 5142-5145;
19. c) V. Bagutski, A. Ros, V. K. Aggarwal, Tetrahedron 2009, 65, 9956-9960. Note that the lithiation/borylation reaction of secondary carbamates requires a phenyl group to acidify the adjacent proton. The use of alkenes in place of aromatic groups is currently being investigated.
20. a) J. M. O'Brien, K.-S. Lee, A. H. Hoveyda, J. Am. Chem. Soc. 2010, 132, 10630-10 633;
21. b) A. Guzman-Martinez, A. H. Hoveyda, J. Am. Chem. Soc. 2010, 132, 10634-10637.
22. a) S.W. Slayden, J. Org. Chem. 1982, 47, 2753-2757;
23. b) S. P. Thomas, R. M. French, V. Jheengut, V. K. Aggarwal, Chem. Rec. 2009, 9, 24.
24. a) D. S. Matteson, D. Majumdar, J. Am. Chem. Soc. 1980, 102, 7588-7590;
25. b) D. S. Matteson, D. Majumdar, Organometallics 1983, 2, 1529-1535;
26. c) H. C. Brown, M. V. Rangaishenvi, S. Jayaraman, Organometallics 1992, 11, 1948-1954.
27. Matteson et al. have reported the homologation of simple primary and secondary boronates: a) D. S. Matteson, Tetrahedron 1998, 54, 10555-10607;
28. b) K. M. Sadhu, D. S. Matteson, Organometallics 1985, 4, 1687-1689;
29. Also see: c) R. H.Wallace, K. K. Zong, Tetrahedron Lett. 1992, 33, 6941-6944;
30. d) R. Soundararajan, G. Li, H. C. Brown, Tetrahedron Lett. 1994, 35, 8957-8960;
31. e) S. Werle, T. Fey, JM. Neudörfl, H.-G. Schmalz, Org. Lett. 2007, 9, 3555-3558.
32. For example, the attempt of the Matteson group to extend their highly stereoselective homologation of boronic esters to tertiary substrates was not successful as homologation reactions were no longer stereospecific and resulted in low diastereoselectivities. D. S. Matteson, G. D. Hurst, Heteroat. Chem. 1990, 1, 65-74.
33. See supporting information for details.
34. P. B. Tripathy, D. S. Matteson, Synthesis 1990, 200-206.
35. According to HSAB theory, it is also possible that the soft nucleophile (carbon) favors reaction with the soft leaving group (Br) whereas the hard nucleophile (oxygen) favors the hard leaving group (Cl). We thank one of the referees for this suggestion.
36. a) G. Zweifel, H. Arzoumanian, C. C. Whitney, J. Am. Chem. Soc. 1967, 89, 3652-3653;
37. b) G. Zweifel, N. L. Polston, C. C.Whitney, J. Am. Chem. Soc. 1968, 90, 6243;
38. c) D. A. Evans, T. C. Crawford, R. C. Thomas, J. A. Walker, J. Org. Chem. 1976, 41, 3947-3953.
39. It is possible that the severe steric hindrance between substituents on the boron atom in 7, together with the Mg salts present, promote ring-opening of the pinacol ester to give an intermediate borinic ester. This electrophilic species can then be attacked by vinylmagnesium bromide again, ultimately leading to borane ate-complex 8.
40. This result is rather surprising since Zweifel found that thexyl and alkenyl groups migrate at similar rates when a bis(alkenyl) thexylborane was treated with I2 and NaOH; see Ref. [11b].
41. a) H. C. Brown, M. V. Rangaishenvi, S. Jayaraman, Organometallics 1992, 11, 1948-1954;
42. b) H. C. Brown, S. Jayaraman, J. Org. Chem. 1993, 58, 6791-6794.
43. Reaction of racemic 2a with racemic 1-chloro-allyllithium gave the same 24:1 ratio of diastereoisomers. This ratio reflects the relative rates of reaction of the two diastereomeric pairs (e.g., R+R vs. R+S) without the intervention of kinetic resolution.
44. CCDC 800577 contains the supplementary crystallographic data for allyl boronic ester 14b. This data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data request/cif.
45. For the shortest (3 steps) asymmetric synthesis of (R)-sporochnol reported to date (e.r.=78.5:21.5), see: a) F. Gao, Y. Lee, K. Mandai, A. H. Hoveyda, Angew. Chem. 2010, 122, 8548-8552;
46. Angew. Chem. Int. Ed. 2010, 49, 8370-8374.
47. For other asymmetric total syntheses of (R)-or (S)-Sporochnol, see: b) Y. Inokoishi, N. Sasakura, K. Nakano, Y. Ichikawa, H. Kotsuki, Org. Lett. 2010, 12, 1616-1619;
48. c) S. Hatakeyama, D. Yanagimoto, K. Kawano, K. Takahashi, J. Ishihara, Heterocycles 2009, 77, 249-253;
49. d) R. Alibés, F. Busquí, G. G. Bardají, P. D. March, M. Figueredo, J. Font, Tetrahedron: Asymmetry 2006, 17, 2632-2636;
50. e) S. Ohira, A. Kuboki, T. Hasegawa, T. Kikuchi, T. Kutsukake, M. Nomura, Tetrahedron Lett. 2002, 43, 4641-4644;
51. f) C. A. Luchaco-Cullis, H. Mizutani, K. E. Murphy, A. H. Hoveyda, Angew. Chem. 2001, 113, 1504-1508;
52. Angew. Chem. Int. Ed. 2001, 40, 1456-1460;
53. g) Y. Kita, A. Furukawa, J. Futamura, K. Ueda, Y. Sawama, H. Hamamoto, H. Fujioka, J. Org. Chem. 2001, 66, 8779-8786;
54. h) A. Fadel, L. Vandromme, Tetrahedron: Asymmetry 1999, 10, 1153-1162;
55. i) M. Takahashi, Y. Shioura, T. Murakami, K. Ogasawara, Tetrahedron: Asymmetry 1997, 8, 1235-1242;
56. j) T. Kamikubo, M. Shimizu, K. Ogasawara, Enantiomer 1997, 2, 297-301.
57. K. Rasmussen, D. O. Calligaro, J. F. Czachura, L. J. Dreshfield- Ahmad, D. C. Evans, S. K. Hemrick-Luecke, M. J. Kallman, W. T. Kendrick, J. D. Leander, D. L. Nelson, C. D. Overshiner, D. B. Wainscott, M. C. Wolff, D. T. Wong, T. A. Branchek, J. M. Zgombick, Y.-C. Xu, J. Pharmacol. Exp. Ther. 2000, 294, 688-700.
58. Y.-C. Shen, P. I. Tsai, W. Fenical, M. E. Hay, Phytochemistry 1993, 32, 71-75.
59. a) S. E. Denmark, J. Fu, M. J. Lawler, J. Org. Chem. 2006, 71, 1523-1536;
60. b) S. E. Denmark, J. Fu, Org. Lett. 2002, 4, 1951-1953.
61. For a discussion of the factors affecting the migratory aptitude of primary, secondary, and tertiary alkyl groups in ate complexes derived from boranes and boronic esters, see: A. Bottoni, M. Lombardo, A. Neri, C. Trombini, J. Org. Chem. 2003, 68, 3397-3405.