Fluorinated alcohols as promoters for the metal-free direct substitution reaction of allylic alcohols with nitrogenated, silylated, and carbon nucleophiles

Journal of Organic Chemistry

Volumn 77, Issue 17, 2012, Pages 7344-7354

  Trillo, Paz ^a   Baeza, Alejandro ^a   Nájera, Carmen ^a  

^a UNIVERSITY OF ALICANTE   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

1 ,3-DICARBONYL COMPOUNDS; 2 ,2 ,2-TRIFLUOROETHANOL; ACETYLACETONE; ALLYLIC ALCOHOL; ALLYLIC SUBSTITUTION; CARBON NUCLEOPHILES; CARBOXAMIDES; ELECTRON-RICH; FLUORINATED ALCOHOL; FRIEDEL-CRAFTS; HIGH YIELD; MELDRUM'S ACIDS; REACTION MEDIA; REACTION PATHWAYS; TRIMETHYLSILANE; TRIMETHYLSILYLAZIDE;

ACETONE; ALLYLATION; AMIDES; ANILINE; CARBON; ELECTRONIC PROPERTIES; ETHANOL; PHENOLS; SUBSTITUTION REACTIONS; SULFUR COMPOUNDS;

NUCLEOPHILES;

ACETYLACETONE; ACETYLENE DERIVATIVE; ALCOHOL DERIVATIVE; AMIDE; AMINE; ANILINE; ANISOLE; CARBAMIC ACID DERIVATIVE; CARBON; INDOLE; NITROGEN; NUCLEOPHILE; PHENOL; SILANE DERIVATIVE; SULFONAMIDE;

ARTICLE; ELECTRON; FLUORINATION; FRIEDEL CRAFTS REACTION; ISOMERIZATION; SILYLATION; STEREOCHEMISTRY; SUBSTITUTION REACTION;

EID: 84866140091     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo301049w     Document Type: Article

References (45)

1. Bégué, J. -P.; Bonnet-Delpon, D.; Crousse, B. Synlett 2004, 18
2. Shuklov, I. A.; Dubrovina, N. V.; Börner, A. Synthesis 2007, 2925
3. Berkessel, A.; Adrio, J. A.; Hüttenhain, D.; Neudörfl, J. M. J. Am. Chem. Soc. 2006, 128, 8421
4. Spanedda, M. V.; Hoang, V. D.; Crousse, B.; Bonnet-Delpon, D.; Bégué, J. -P. Tetrahedron Lett. 2003, 44, 217
5. Di Salvo, A.; Spanedda, M. V.; Ourévitch, M.; Crousse, B.; Bonnet-Delpon, D. Synthesis 2003, 2231
6. Das, U.; Crousse, B.; Kesavan, V.; Bonnet-Delpon, D.; Bégué, J. -P. J. Org. Chem. 2000, 65, 6749
7. More recently the stereoselective and regioselective ring opening of chiral epoxides with indoles and pyrroles has been reported: Westermaier, M.; Mayr, H. Chem. - Eur. J. 2008, 14, 1638
8. De, K.; Legros, J.; Crousse, B.; Bonnet-Delpon, D. J. Org. Chem. 2009, 74, 6260
9. Muzart, J. Eur. J. Org. Chem. 2007, 3077
10. Muzart, J. Tetrahedron 2008, 64, 5815
11. Emer, E.; Sinisi, R.; Guiteras-Capdevila, M.; Petruzzielo, D.; De Vicentiis, F.; Cozzi, P. G. Eur. J. Org. Chem. 2011, 647
12. Bandini, M. Angew. Chem., Int. Ed. 2011, 50, 994
13. Biannic, B.; Aponick, A. Eur. J. Org. Chem. 2011, 6605
14. Giner, X.; Trillo, P.; Nájera, C. J. Organomet. Chem. 2010, 696, 357
15. Trillo, P.; Baeza, A.; Nájera, C. Eur. J. Org. Chem. 2012, 2929
16. During the preparation of this manuscript an asymmetric α -alkylation of aldehydes with benzylic alcohols in fluorinated alcohols was reported: Xiao, J.; Zhao, K.; Loh, T.-P. Chem. Commun. 2012, 48, 3548
17. N1 reaction of benzylic alcohols mediated by water, see: Cozzi, P. G.; Zoli, L. Angew. Chem., Int. Ed. 2008, 47, 4162
18. The use of more basic amines seems to be restricted to processes involving π-allylmetal complexes. Thus, palladium and platinum complexes have been used for this purpose. For examples of palladium-catalyzed allylic substitution reaction with basic amines, see ref 6a. For a recent example of the use of platinum-based catalyst, see: Ohshima, T.; Miyamoto, Y.; Ipposhi, J.; Nakahara, Y.; Utsunomiya, M.; Mashima, K. J. Am. Chem. Soc. 2009, 131, 14317
19. Recently an azidation of allylic alcohols catalyzed by AgOTf has been reported; see: Rueping, M.; Vila, C.; Uria, U. Org. Lett. 2012, 14, 768
20. March, J. Advanced Organic Chemistry: Reactions, Mechanism and Structure, 4 th ed.; John Wiley & Sons: New York, 1992; p 560. For selected recent examples, see
21. Anderson, L. L.; Arnold, J.; Bergman, R. G. J. Am. Chem. Soc. 2005, 127, 14542
22. Magnus, P.; Turnbull, R. Org. Lett. 2006, 8, 3497
23. Motokura, K.; Nakagiri, N.; Mizugaki, T.; Ebitani, K.; Kaneda, K. J. Org. Chem. 2007, 72, 6006 and references therein
24. The enantioenriched alcohol (S)- 1b was obtained according to a described procedure; for details, see: Fernández-Mateos, E.; Maciá, B.; Ramó?n, D. J.; Yus, M. Eur. J. Org. Chem. 2011, 6851. The amination product 3ba was analyzed by HPLC. The corresponding fluoroalkyl ethers obtained as byproducts were also isolated as racemic mixtures in both cases
25. This isomerization of alcohol 1c has been observed by us (see ref 7b) and by others; see: McCubbin, J. A.; Voth, S.; Krokhin, O. V. J. Org. Chem. 2011, 76, 8537
26. Baudoux, J.; Perrigand, K.; Madec, P. J.; Gaumont, A. C.; Dez, I. Green Chem. 2007, 9, 1346
27. Cimarelli, C.; Palmieri, G. Tetrahedron: Asymmetry 2000, 11, 2555
28. Ohta, T.; Sasayama, H.; Nakajima, O.; Kurahashi, N.; Fujii, T.; Fukukama, I. Tetrahedron: Asymmetry 2003, 14, 537
29. Yang, H.; Fang, L.; Zhang, M. Eur. J. Org. Chem. 2009, 666
30. Kabalka, G. W.; Yao, M. L.; Borella, S. Org. Lett. 2006, 8, 879
31. Alacid, E.; Nájera, C. Org. Lett. 2008, 10, 5011
32. Liu, P. N.; Zhon, Z. Y.; Lau, C. P. Chem. - Eur. J. 2007, 13, 8610
33. Ross, J.; Chen, W.; Xu, L.; Xiao, J. Organometallics 2001, 20, 138
34. Haslego, M. L.; Smith, F. X. Synth. Commun. 1980, 10, 421
35. Haight, A. R.; Stoner, E. J.; Peterson, M. J.; Grover, V. K. J. Org. Chem. 2003, 68, 8092
36. Pyne, S. G.; Dong, Z. J. Org. Chem. 1996, 61, 5517
37. Yamamoto, H.; Ho, E.; Sasaki, I.; Mitsutake, M.; Takagi, Y.; Imagawa, H.; Nishizawa, M. Eur. J. Org. Chem. 2011, 2417
38. Liao, L.; Sigman, M. S. J. Am. Chem. Soc. 2010, 132, 10209
39. Malkov, A. V.; Davis, S. L.; Baxendale, I. R.; Mitchell, W. L.; Kocovsky, P. J. Org. Chem. 1999, 64, 2751
40. Meyer, V. J.; Niggemann, M. Eur. J. Org. Chem. 2011, 3671
41. Sanz, R.; Martí?nez, A.; Miguel, D.; álvarez-Gutierrez, J. M. Adv. Synth. Catal. 2006, 348, 1841
42. Zhu, A.; Li, L.; Wang, J.; Zhuo, K. Green. Chem. 2011, 13, 1244
43. Ohshima, T.; Nakahara, Y.; Ipposhi, J.; Miyamoto, Y.; Mashima, K. Chem. Commun. 2011, 8322
44. Sreedhar, B.; Ravi, V.; Yada, D. Tetrahedron Lett. 2011, 52, 1208
45. Giner, X.; Nájera, C. Org. Lett. 2008, 10, 2119