The productive merger of iodonium salts and organocatalysis: A non-photolytic approach to the enantioselective α-trifluoromethylation of aldehydes

Journal of the American Chemical Society

Volumn 132, Issue 14, 2010, Pages 4986-4987

  Allen, Anna E ^a   MacMillan, David W C ^a  

^a PRINCETON UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDES; CATALYSIS; MERGING; RATE CONSTANTS;

AGROCHEMICAL APPLICATION; ENANTIOSELECTIVE; ENANTIOSELECTIVE CONSTRUCTION; ORGANOCATALYSIS; ORGANOCATALYTIC; SIMPLE PROTOCOL; TRIFLUOROMETHYL; TRIFLUOROMETHYLATION;

ENANTIOSELECTIVITY;

ALDEHYDE DERIVATIVE; IODINE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENANTIOMER; LIPOPHILICITY; METHYLATION; OXIDATION; REACTION ANALYSIS; STEREOSPECIFICITY;

EID: 77950854848     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja100748y     Document Type: Article

References (23)

1. Chambers, R. D. Fluorine in Organic Chemistry; Wiley: New York, 1973.
2. Banks, R. E., Smart, B. E., and Tatlow, J. C. Organofluorine Chemistry: Principles and Commercial Applications; Plenum Press: New York, 1994.
3. Filler, R., Kobayashi, Y., and Yagupolskii, L. M. Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications; Elsevier: New York, 1993
4. MuÌller, K., Faeh, C., and Diederich, F. Science 2007, 317, 1881
5. Pursor, S., Moore, P. R., Swallow, S., and Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320
6. Nagib, D. A., Scott, M. E., and MacMillan, D. W. C. J. Am. Chem. Soc. 2009, 131, 10875
7. Noritake, S., Shibata, N., Nomura, Y., Huang, Y., Matsnev, A., Nakamura, S., Toru, T., and Cahard, D. Org. Biomol. Chem. 2009, 7, 3599
8. For seminal reports on Tognis reagent and its applications, see: Eisenberger, P., Gischig, S., and Togni, A. Chem.î - Eur. J. 2006, 12, 2579
9. Kieltsch, I., Eisenberger, P., and Togni, A. Angew. Chem., Int. Ed. 2007, 46, 754
10. Eisenberger, P., Kieltsch, I., Armanino, N., and Togni, A. Chem. Commun. 2008, 1575
11. Kieltsch, I., Eisenberger, P., Stanek, K., and Togni, A. Chimia 2008, 62, 260
12. Koller, R., Stanek, K., Stolz, D., Aardoom, R., Niedermann, K., and Togni, A. Angew. Chem., Int. Ed. 2009, 48, 4332
13. For seminal contributions toward other electrophilic trifluoromethylating sources, see: Yagupolskii, L. M., Kondratenko, N. V., and Timofeeva, G. N. J. Org. Chem. USSR (Engl. Transl.) 1984, 20, 103
14. Umemoto, T. and Ishihara, S. Tetrahedron Lett. 1990, 31, 3579
15. Umemoto, T. and Ishihara, S. J. Am. Chem. Soc. 1993, 115, 2156
16. Umemoto, T. Chem. Rev. 1996, 96, 1757
17. Imidazolidinone 3 can be purchased from Sigma-Aldrich as the hydrochloric acid salt (CAS no. 278173-23-2). The hydrochloric acid salt was converted to the trifluoroacetic acid salt before use in this protocol.
18. 3,3-Dimethyl-1-trifluoromethyl-1,2-benziodoxole can be handled in moist air without any special precautions. However, it should be stored at -20 °C to prevent slow degradation over time (see ref 3a).
19. An alternate mechanism wherein Tognis reagent might participate in a redox one-electron alkylation pathway was also considered initially.
20. Eastman, K. and Baran, P. S. Tetrahedron 2009, 65, 3149
21. Beeson, T. D. and MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 8826
22. Brochu, M. P., Brown, S. P., and MacMillan, D. W. C. J. Am. Chem. Soc. 2004, 126, 4108
23. Time studies showed erosion of enantiopurity over time, and the use of tert -amyl alcohol appeared to impede this post-reaction racemization.