Catalytic enantioselective construction of β-quaternary carbons via a conjugate addition of cyanide to β,β-disubstituted α,β-unsaturated carbonyl compounds

Journal of the American Chemical Society

Volumn 132, Issue 26, 2010, Pages 8862-8863

  Tanaka, Yuta ^a   Kanai, Motomu ^a   Shibasaki, Masakatsu ^a,b  

^a UNIVERSITY OF TOKYO   (Japan)

^b INSTITUTE OF MICROBIAL CHEMISTRY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYLATION; CYANIDES; ENANTIOSELECTIVITY; KETONES; STRONTIUM; UNSATURATED COMPOUNDS;

ACTIVE CATALYST; CATALYTIC ENANTIOSELECTIVE CONSTRUCTION; CHIRAL LIGAND; CONJUGATE ADDITION; CYANATION; CYANATION REACTION; ENANTIOSELECTIVE; ENANTIOSELECTIVE CONJUGATE ADDITION; QUATERNARY CARBON; STRONTIUM COMPLEXES; TRIMETALLIC; UNSATURATED CARBONYL COMPOUNDS; UNSATURATED KETONES;

CATALYSTS;

CARBON; CARBONYL DERIVATIVE; CYANIDE; KETONE DERIVATIVE; PYRROLE DERIVATIVE; STRONTIUM; KETONE; NITRILE;

ARTICLE; CATALYST; CHIRALITY; CONJUGATE; CONTROLLED STUDY; CYANATION; ELECTROSPRAY MASS SPECTROMETRY; ENANTIOSELECTIVITY; CATALYSIS; CHEMISTRY; ENZYME SPECIFICITY; STEREOISOMERISM;

CARBON; CATALYSIS; KETONES; NITRILES; PYRROLES; STEREOISOMERISM; SUBSTRATE SPECIFICITY;

EID: 77954247593     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja1035286     Document Type: Article

References (30)

1. Trost, B. M. and Jiang, C. Synthesis 2006, 369
2. Cozzi, P. G., Hilgraf, R., and Zimmermann, N. Eur. J. Org. Chem. 2007, 36, 5969
3. For selected examples, see: Hird, A. W. and Hoveyda, A. H. J. Am. Chem. Soc. 2005, 127, 14988
4. dAugustin, M., Palais, L., and Alexakis, A. J. Angew. Chem., Int. Ed. 2005, 44, 1376
5. Fillion, E. and Wilsily, A. J. Am. Chem. Soc. 2006, 128, 2774
6. Shintani, R., Tsutsumi, Y., Nagaosa, M., Nishimura, T., and Hayashi, T. J. Am. Chem. Soc. 2009, 131, 13588
7. Matsumoto, Y., Yamada, K., and Tomioka, K. J. Org. Chem. 2008, 73, 4578 See Supporting Information (SI) for further references.
8. Sammis, G. M. and Jacobsen, E. N. J. Am. Chem. Soc. 2003, 125, 4442
9. Sammis, G. M., Danjo, H., and Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 9928
10. Mazet, C. and Jacobsen, E. N. Angew. Chem., Int. Ed. 2008, 47, 1762
11. Mita, T., Sasaki, K., Kanai, M., and Shibasaki, M. J. Am. Chem. Soc. 2005, 127, 514
12. Fujimori, I., Mita, T., Maki, K., Shiro, M., Sato, A., Furusho, S., Kanai, M., and Shibasaki, M. Tetrahedron 2007, 63, 5820
13. Tanaka, Y., Kanai, M., and Shibasaki, M. J. Am. Chem. Soc. 2008, 130, 6072
14. Wang, J., Li, W., Liu, Y., Chu, Y., Lin, L., Liu, X., and Feng, X. Org. Lett. 2010, 12, 1280
15. For a catalytic enantioselective (up to 72% ee) conjugate addition of cyanide to β,β-disubstituted nitroalkenes, see
16. Bernardi, L., Fini, F., Fochi, M., and Ricci, A. Synlett 2008, 1857
17. 2. See SI.
18. For the use of chiral Sr catalysts, see: Agostinho, M. and Kobayashi, S. J. Am. Chem. Soc. 2008, 130, 2430
19. Kobayashi, S., Yamaguchi, M., Agostinho, M., and Schneider, U. Chem. Lett. 2009, 38, 296
20. An alkaline earth metal (Ba)- 1 complex is an effective asymmetric catalyst for a Diels-Alder reaction: Yamatsugu, K., Yin, L., Kamijo, S., Kimura, Y., Kanai, M., and Shibasaki, M. Angew. Chem., Int. Ed. 2009, 48, 1070
21. For the importance of the higher-order structure of multimetallic asymmetric catalysts, see: Kato, N., Mita, T., Kanai, M., Therrien, B., Kawano, M., Yamaguchi, K., Danjo, H., Sei, Y., Sato, A., Furusho, S., and Shibasaki, M. J. Am. Chem. Soc. 2006, 128, 6768
22. For more details on optimization studies, see SI.
23. The consistent enantioselectivity (97 ee) was produced using TBSCN or TMSCN + 2,6-dimethylphenol, HCN, or TMSCN + MeOH as cyanating reagents in the presence of 10 mol catalyst. Therefore, HCN should be the stoichiometric cyanide source in this reaction.
24. When the catalyst loading was 0.5 mol %, however, the use of TMSCN instead of TBSCN produced markedly lower enantioselectivity (50% ee). The concentration of HCN was much higher when using TMSCN than TBSCN in the presence of 2,6-dimethylphenol. A large excess of HCN would partially decompose the catalyst, leading to the significant difference in enantioselectivity especially when the catalyst loading was lowered.
25. Matsunaga, S., Kinoshita, T., Okada, S., Harada, S., and Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 7559
26. Evans, D. A., Borg, G., and Scheidt, K. A. Angew. Chem., Int. Ed. 2002, 41, 3188
27. For synthetically useful conversions of the products, see SI.
28. The 1,2-adducts were not detected in any cases by TLC analysis during the reaction course. For previous examples in which 1,4-cyanation products were produced from kinetically formed 1,2-adducts via cyanide migration, see
29. Nagata, W. and Yoshioka, M. Org. React. 1977, 25, 255 and ref 3f
30. A crossover experiment revealed that this rearrangement was an intermolecular process. See SI.