Enantioselective synthesis of SM-130686 based on the development of asymmetric Cu(I)F catalysis to access 2-oxindoles containing a tetrasubstituted carbon

Journal of the American Chemical Society

Volumn 131, Issue 20, 2009, Pages 6946-6948

  Tomita, Dalsuke ^a   Yamatsugu, Kenzo ^a   Kanai, Motomu ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENYL; ALKENYLATION; ARYLATIONS; ASYMMETRIC REACTION; BIOLOGICALLY ACTIVE COMPOUNDS; CATALYTIC AMOUNTS; ENANTIOSELECTIVE; ENANTIOSELECTIVE APPROACH; ENANTIOSELECTIVE SYNTHESIS; GROWTH HORMONES; INTERMOLECULAR REACTIONS; INTRAMOLECULAR REACTIONS; NATURAL PRODUCTS; ORALLY ACTIVE; OXINDOLES; SILICA GEL COLUMN CHROMATOGRAPHY; STERICALLY CONGESTED;

AMIDES; AROMATIC COMPOUNDS; CHELATION; CHROMATOGRAPHIC ANALYSIS; COLUMN CHROMATOGRAPHY; CONDENSATION REACTIONS; SILICA; SILICA GEL;

COMPLEXATION;

CARBON; COPPER; GROWTH HORMONE SECRETAGOGUE; OXINDOLE; SM 130686; UNCLASSIFIED DRUG; ETHYLAMINE; FLUORIDE; INDOLE DERIVATIVE;

ARTICLE; ARYLATION; ASYMMETRIC CATALYSIS; CATALYST; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; ENANTIOSELECTIVITY; SYNTHESIS; CATALYSIS; CHEMISTRY; STEREOISOMERISM;

CATALYSIS; COPPER; ETHYLAMINES; FLUORIDES; INDOLES; STEREOISOMERISM;

EID: 70349125916     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja901995a     Document Type: Article

References (32)

1. (a) Tokunaga, T.; Hume, W. E.; Umezome, T.; Okazaki, K.; Ueki, Y.; Kumagai, K.; Hourai, S.; Nagamine, J.; Seki, H.; Taiji, M.; Noguchi, H.; Nagata, R. J. Med. Chem. 2001, 44, 4641.
2. (b) Tokunaga, T.; Hume, W. E.; Nagamine, J.; Kawamura, T.; Taiji, M.; Nagata, R. Bioorg. Med. Chem. Lett. 2005, 75, 1789.
3. On an industrial scale, pharmaceuticals that are not derived from natural sources containing chiral tetrasubstituted carbons are almost always produced through resolution, which clearly indicates the inadequacy of the current synthetic methods for producing such chiral building blocks on a large scale with sufficient environmental friendliness. See the Supporting Information (SI) for typical examples.
4. Rh- or Pd-catalyzed asymmetric addition of arylboronic acids to isatins: (a) Shintani, R.; Inoue, M.; Hayashi, T. Angew. Chem., Int. Ed. 2006, 45, 3353.
5. (b) Roullec, P. Y.; Jagt, R. B. C.; de Vries, J. G.; Feringa, B. L.; Minnaard, A. J. Org. Lett. 2006, 5, 2715.
6. (c) Lai, H.; Huang, Z.; Wu, Q.; Qin, Y. J. Org. Chem. 2009, 74, 283.
7. Benzylic hydroxylation of 2-oxindoles: (d) Ishimaru, T.; Shibata, N.; Nagai, J.; Nakamura, S.; Toru T.; Kanemasa, S. J. Am. Chem. Soc. 2006, 128, 16488.
8. Intramolecular Hartwig-Buchwald arylation of a-methoxy-substituted amides: (e) Jia, Y. X.; Hillgren, J. M.; Watson, E. L.; Marsden, S. P.; Kündig, P. Chem. Commun. 2008, 4040.
9. Other examples of catalytic asymmetric reactions that provide 3-tetrasubstituted-2-oxindols: (a) Trost, B. M.; Frederiksen, M. U. Angew. Chem., Int. Ed. 2005, 44, 308.
10. (b) Duffey, T. A.; Shaw, S. A.; Vedejs, E. J. Am. Chem. Soc. 2009, 131, 14.
11. (c) Kündig, P.; Seidel, T. M.; Jia, Y.; Bernardinelli, G. Angew. Chem., Int. Ed. 2007, 46, 8484.
12. (d) Hills, I. D.; Fu, G. C. Angew. Chem., Int. Ed. 2003, 42, 3921.
13. (e) Dounay, A. B.; Hatanaka, K.; Kodanko, J. J.; Oestreich, M.; Overman, L. E.; Pfeifer, L. A.; Weiss, M. M. J. Am. Chem. Soc. 2003, 125, 6261.
14. (a) Tomita, D.; Wada, R.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2005, 127, 4138.
15. (b) Motoki, R.; Tomita, D.; Kanai, M.; Shibasaki, M. Tetrahedron Lett. 2006, 47, 8083.
16. Tomita, D.; Kanai, M.; Shibasaki, M. Chem. - Asian J. 2006, 7, 161.
17. n., n ≥ 2] through dynamic ligand exchange on silicon atoms. The polyfluorinated silicon facilitated silyl trapping of intermediate copper alkoxides (generated via addition of organocopper to carbonyl substrates; see ref 5a), the initial event in turnoverlimiting regeneration of the organocopper species. For the proposed catalytic cycle in the presence of a fluoride additive, see the SI. For the mechanism of relevant acceleration effects of metal fluoride additives in the CuFcatalyzed asymmetric aldol reaction of ketones, see: Oisaki, K.; Zhao, D.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2006, 128, 7164.
18. The difference in reactivity between silicon- and boron-based nucleophiles in CuF catalysis might be due to the difference in the electronegativities of silicon and boron atoms (1.74 and 2.01, respectively, on the Allred and Rochow scale: Cotton, F. A.; Wilkinson, G.; Gauss, P. L. Basic Inorganic Chemistry; Wiley: New York, 1995). The alkoxide ligand transfer from the intermediate copper alkoxide to the more positive silicon atoms would be faster than that to boron atoms.
19. Gulliner, D. J.; Levason, W.; Webster, M. Inorg. Chim. Acta 1981, 52, 153.
20. The reactivity was markedly lower in the absence of TBAT additive (0-16% yield).
21. (a) Ireland, T.; Tappe, K.; Grossheimann, G.; Knochel, P. Chem. - Eur. J. 2002, 5, 843.
22. (b) Fukuzawa, S.; Yamamoto, M.; Hosaka, M.; Kikuchi, S. Eur. J. Org. Chem. 2007, 5540.
23. See the SI for details.
24. 3 complex, yield = ±5%, ee = ±1%].
25. Pietraszuk, C.; Fischer, H.; Kujiwa, M.; Marciniec, B. Tetrahedron Lett. 2001, 42, 1175.
26. A Pd-catalyzed enantioselective intramolecular arylation of ketones to produce 3-tetrasubstituted dihydrobenzofurans has been reported: Liu, G.; Lu, X. J. Am. Chem. Soc. 2006, 128, 16504.
27. Ligand 12 was not suitable for the intermolecular arylation; 8dc was obtained in only 11% ee using 10 mol % CuF-12 [90% yield; compare with 96% ee using CuF-6 (Table 2, entry 9)].
28. Léon, G.; Cécile, F.; Frédéric, D.; Claire, C.; Roland, T. Can. J. Chem. 2001, 79, 1827.
29. (a) Boler, T. M.; Murphy, J. M.; Hapke, M.; Ishiyama, T.; Miyaura, N.; Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 14263.
30. (b) Murphy, J. M.; Liao, X.; Hartwig, J. H. J. Am. Chem. Soc. 2007, 129, 15434.
31. Kianmehr, E.; Yahyaee, M.; Tabatabai, K. Tetrahedron Lett. 2007, 48, 2713.
32. Ottenheijm, H. C. J.; de Man, J. H. M. Synthesis 1975, 163.