Direct organocatalytic α-fluorination of aldehydes and ketones

Synlett

Volumn , Issue 6, 2005, Pages 991-993

  Enders, Dieter ^a   Hüttl, Matthias R M ^a  

^a RWTH AACHEN UNIVERSITY   (Germany)

Author keywords

Aldehydes; Electrophilic fluorination; Ketones; Organocatalysis; Selectfluor

Indexed keywords

1 CHLOROMETHYL 4 FLUORO 1,4 DIAZONIABICYCLO[2.2.2]OCTANE BIS(TETRAFLUOROBORATE); ALDEHYDE DERIVATIVE; BORIC ACID; FLUORINE DERIVATIVE; KETONE DERIVATIVE; PROLINE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; ENANTIOMER; ENANTIOSELECTIVITY; FLUORINATION; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 17144415210     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2005-864813     Document Type: Article

References (43)

1. (a) Shimizu, M.; Hiyama, T. Angew. Chem. Int. Ed. 2005, 44, 214; Angew. Chem. 2005, 117, 218.
2. (a) Shimizu, M.; Hiyama, T. Angew. Chem. Int. Ed. 2005, 44, 214; Angew. Chem. 2005, 117, 218.
3. (b) Welch, J. T.; Eswarakrishnan, S. Fluorine in Bioorganic Chemistry; Wiley: New York, 1991.
4. Enantiocontrolled Synthesis of Fluoro-Organic Compounds. Stereochemical Challenges and Biomedicinal Targets; Soloshonok, V. A., Ed.; Wiley: New York, 1999.
5. Chambers, R. D. Fluorine in Organic Chemistry; Blackwell: Oxford, 2004.
6. For recent reviews on electrophilic fluorination, see: (a) Ma, J.-A.; Cahard, D. Chem. Rev. 2004, 104, 6119.
7. (b) Ibrahim, H.; Togni, A. Chem. Commun. 2004, 1147.
8. (c) Lal, G. S.; Pez, G. P.; Syvret, R. G. Chem. Rev. 1996, 96, 1737.
9. (d) Taylor, S. D.; Kotoris, C. C.; Hum, G. Tetrahedron 1999, 55, 12431.
10. (e) Muniz, K. In Organic Synthesis Highlights V; Schmalz, H.-G.; Wirth, T., Eds.; Wiley-VCH: Weinheim, 2003.
11. (a) Singh, R. P.; Shreeve, J. M. Acc. Chem. Res. 2004, 37, 31.
12. (b) Nyffeler, P. T.; Duron, S. G.; Burkart, M. D.; Vincent, S. P.; Wong, C.-H. Angew. Chem. Int. Ed. 2005, 44, 192; Angew. Chem. 2005, 117, 196.
13. (b) Nyffeler, P. T.; Duron, S. G.; Burkart, M. D.; Vincent, S. P.; Wong, C.-H. Angew. Chem. Int. Ed. 2005, 44, 192; Angew. Chem. 2005, 117, 196.
14. (a) Hintermann, L.; Togni, A. Angew. Chem. Int. Ed. 2000, 39, 4359; Angew. Chem. 2000, 112, 4530.
15. (a) Hintermann, L.; Togni, A. Angew. Chem. Int. Ed. 2000, 39, 4359; Angew. Chem. 2000, 112, 4530.
16. (b) Frantz, R.; Hintermann, L.; Perseghini, M.; Broggini, D.; Togni, A. Org. Lett. 2003, 5, 1709.
17. (c) Togni, A.; Mezzetti, A.; Barthazy, P.; Becker, C.; Devillers, I.; Frantz, R.; Hintermann, L.; Perseghini, M.; Sanna, M. Chimia 2001, 55, 801.
18. (a) Hamashima, Y.; Yagi, K.; Takano, H.; Tamás, L.; Sodeoka, M. J. Am. Chem. Soc. 2002, 124, 14530.
19. (b) Hamashima, Y.; Yagi, K.; Takano, H.; Hotta, D.; Sodeoka, M. Org. Lett. 2003, 5, 3225.
20. (c) Ma, J.-A.; Cahard, D. Tetrahedron: Asymmetry 2004, 15, 1007.
21. (d) Shibata, N.; Ishimaru, T.; Nagai, T.; Kohno, J.; Toru, T. Synlett 2004, 1703.
22. (a) Kim, D. Y.; Park, E. J. Org. Lett. 2002, 4, 545.
23. (b) For the α-fluorination of cyclic ketones to quaternary stereogenic centers with stoichiometric amounts of cinchona alkaloids, see: Shibata, N.; Suzuki, E.; Asahi, T.; Shiro, M. J. Am. Chem. Soc. 2001, 123, 7001.
24. (c) Shibata, N.; Suzuki, E.; Takeuchi, Y. J. Am. Chem. Soc. 2000, 122, 10728.
25. (d) Cahard, D.; Audouard, C.; Plaquevent, J.-C.; Roques, N. Org. Lett. 2000, 2, 3699.
26. (a) Marigo, M.; Bachmann, S.; Halland, N.; Braunton, A.; Jørgensen, K. A. Angew. Chem. Int. Ed. 2004, 43, 5507; Angew. Chem. 2004, 116, 5623.
27. (a) Marigo, M.; Bachmann, S.; Halland, N.; Braunton, A.; Jørgensen, K. A. Angew. Chem. Int. Ed. 2004, 43, 5507; Angew. Chem. 2004, 116, 5623.
28. (b) Halland, N.; Braunton, A.; Bachmann, S.; Marigo, M.; Jørgensen, K. A. J. Am. Chem. Soc. 2004, 126, 4790.
29. (c) Marigo, M.; Kumaragurubaran, N.; Jørgensen, K. A. Chem.-Eur. J. 2004, 10, 2133.
30. (d) Brochu, M. P.; Brown, S. P.; MacMillan, D. W. C. J. Am. Chem. Soc. 2004, 126, 4108.
31. (e) Wack, H.; Taggi, A. E.; Hafez, A. M.; Drury, W. J. III; Lectka, T. J. Am. Chem. Soc. 2001, 123, 1531.
32. Mase, N.; Tanaka, F.; Barbas, C. F. III Angew. Chem. Int. Ed. 2004, 43, 2420; Angew. Chem. 2004, 116, 2474.
33. Mase, N.; Tanaka, F.; Barbas, C. F. III Angew. Chem. Int. Ed. 2004, 43, 2420; Angew. Chem. 2004, 116, 2474.
34. General Procedure for the Preparation of α-Fluoroaldehydes and α-Fluoroketones. To a stirred mixture of carbonyl compound 1 (1.0 mmol) and (S)-proline 3a (0.3 mmol) in MeCN (2 mL) was added Selectfluor (1.5 mmol) in one portion at 0 °C. Afterwards trifluoro acetic acid (0.3 mmol) was added and the reaction mixture was stirred at r.t. (0 °C in case of the aldehydes) until the reaction was complete (monitored by GC). Purification by flash chromatography or filtration through a short silica plug, respectively, afforded the pure product 2.
35. Purrington, S. T.; Lazaridis, N. V.; Bumgardner, C. L. Tetrahedron Lett. 1986, 27, 2715.
36. 4 (2.0 mmol) were subsequently added. The mixture was stirred until complete conversion (monitored by TLC), followed by evaporation of the solvents. Purification of the crude product by flash chromatography afforded the pure β-fluoroalcohols.
37. 15
38. Takeuchi, Y.; Nagata, K.; Koizumi, T. J. Org. Chem. 1989, 54, 5453.
39. 17
40. (a) Enders, D.; Potthoff, M. Dissertation; RWTH Aachen: Germany, 1997.
41. (b) Enders, D.; Potthoff, M.; Raabe, G.; Runsink, J. Angew. Chem., Int. Ed. Engl. 1997, 36, 2362; Angew. Chem. 1997, 109, 2454.
42. (b) Enders, D.; Potthoff, M.; Raabe, G.; Runsink, J. Angew. Chem., Int. Ed. Engl. 1997, 36, 2362; Angew. Chem. 1997, 109, 2454.
43. (c) Enders, D.; Faure, S.; Potthoff, M.; Runsink, J. Synthesis 2001, 230.