Amination of allylic alcohols in water at room temperature

Organic Letters

Volumn 11, Issue 11, 2009, Pages 2377-2379

  Nishikata, Takashi ^a   Lipshutz, Bruce H ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; AMINE; PALLADIUM; WATER;

AMINATION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; COMBINATORIAL CHEMISTRY; STEREOISOMERISM; SYNTHESIS; TEMPERATURE;

ALLYL COMPOUNDS; AMINATION; AMINES; CATALYSIS; COMBINATORIAL CHEMISTRY TECHNIQUES; MOLECULAR STRUCTURE; PALLADIUM; STEREOISOMERISM; TEMPERATURE; WATER;

EID: 66149171361     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol900235s     Document Type: Article

References (36)

1. Recent reviews: Herrerías, C. I.; Yao, X.; Li, Z.; Li, C.-J. Chem. Rev. 2007, 107, 2546.
2. Bergman, R. G. Nature 2007, 446, 391.
3. Godula, K.; Sames, D. Science 2006, 312, 67.
4. Ishiyama, T.; Miyaura, N. Pure Appl. Chem. 2006, 78, 1369. See recent allylic C-H aminations:
5. Reed, S. A.; White, M. C. J. Am. Chem. Soc. 2008, 130, 3316.
6. Liu, G.; Yin, G.; Wu, L. Angew. Chem., Int. Ed. 2008, 47, 4733.
7. C-Cl bonds: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed.2002, 41, 4176. C-F bonds:
8. Terao, J.; Todo, H.; Watabe, H.; Ikumi, A.; Shinohara, Y.; Kambe, N. Pure Appl. Chem. 2008, 80, 941.
9. Netherton, M. R.; Fu, G. C. In Topics in Organometallic Chemistry: Palladium in Organic Synthesis; Tsuji, J. Ed.; Springer-Verlag: Germany, 2005; pp 85-108.
10. Muzart, J. Eur. J. Org. Chem. 2007, 3077, and references cited therein.
11. Tamaru, Y. Eur. J. Org. Chem. 2005, 2647.
12. Liu, H.; Liang, X.; Søhel, H.; Bülow, A.; Bols, M. J. Am. Chem. Soc. 2001, 123, 5116.
13. Bower, J. F.; Jumnah, R.; Williams, A. C.; Williams, J. M. J. J. Chem. Soc., Perkin Trans. 1 1997, 1411.
14. Burgess, K.; Liu, L. T.; Pal, B. J. Org. Chem. 1993, 58, 4758.
15. Cheikh, R. B.; Chaabouni, R.; Laurent, A.; Mison, P.; Nafti, A. Synthesis 1983, 685.
16. Reactions in aqueous solution at reflux: Komiya, S.; Hirano, M.; Komine, N.; Hirahara, S. Jpn. Kokai Tokkyo Koho, JP 2005075728; Chem. Abstr. 2005, 253606.
17. Kinoshita, H.; Shinokubo, H.; Oshima, K. Org. Lett. 2004, 6, 4085. Reactions in only water at reflux:
18. Yang, S.-C.; Hsu, Y.-C.; Gan, K.-H. Tetrahedron 2006, 62, 3949.
19. Yokoyama, Y.; Hikawa, H.; Mitsuhashi, M.; Uyama, A.; Hiroki, Y.; Murakami, Y. Eur. J. Org. Chem. 2004, 1244. Yokoyama, Y.; Takagi, N.; Hikawa, H.; Kaneko, S.; Tsubaki, N.; Okuno, H. Adv. Synth. Catal. 2007, 349, 662.
20. Yamashita, Y.; Gopalarathnam, A.; Hartwig, J. F. J. Am. Chem. Soc.2007, 129, 7508.
21. Usui, I.; Schmidt, S.; Keller, M.; Breit, B. Org. Lett. 2008, 10, 1207.
22. Dubs, C.; Yamamoto, T.; Inagaki, A.; Akita, M. Organometallics2006, 25, 1359.
23. Piechaczyk, O.; Doux, M.; Ricard, L.; Le Floch, P. Organometallics 2005, 24, 1204.
24. Liang, H.; Ito, S.; Yoshifuji, M. Org. Lett. 2004, 6, 425.
25. Ozawa, F.; Okamoto, H.; Kawagishi, S.; Yamamoto, S.; Minami, T.; Yoshifuji, M. J. Am. Chem. Soc. 2002, 124, 10968. See also ref 6b.
26. Friedel-Crafts-type reaction: Jana, U.; Maiti, S.; Biswas, S. Tetrahedron Lett. 2008, 49, 858. See also: Shirakawa, S.; Shimizu, S. Synlett2008, 1539.
27. Utsunomiya, M.; Miyamoto, Y.; Ipposhi, J.; Ohshima, T.; Mashima, K. Org. Lett. 2007, 9, 3371.
28. Defieber, C.; Ariger, M. A.; Moriel, P.; Carreira, E. M. Angew. Chem., Int. Ed. 2007, 46, 3139.
29. PTS is available from Sigma-Aldrich, catalog no. 698717.
30. Lipshutz, B. H.; Taft, B. R. Org. Lett. 2008, 10, 1329.
31. Lipshutz, B. H.; Chung, D. W.; Rich, B. Org. Lett. 2008, 10, 3793.
32. Lipshutz, B. H.; Ghorai, S. Aldrichim. Acta 2008, 41, 58.
33. Stuetz, A.; Georgopoulos, A.; Granitzer, W.; Petranyi, G.; Berney, D. J. Med. Chem. 1986, 29, 112.
34. Also supported by observations en route to nafitifine (Scheme 2).
35. DFT calculations for direct allylic substitution reactions with allylic alcohols: Piechaczyk, O.; Thoumazet, C.; Jean, Y.; Le Floch, P. J. Am. Chem. Soc. 2006, 128, 14306. See also ref 6b.
36. Typical Procedure. Allylic alcohol 1 (0.75 mmol), amine 2 (0.5 mmol), dppf (0.025 mmol, 5 mol %), K2CO3 (1.5 mmol), and [Pd(allyl)Cl]2 (0.0125 mmol, 2.5 mol %) were sequentially added under argon to a reaction tube equipped with a stir bar and a septum. PTS solution (1.0 mL, 2 wt %) and HCO2Me (0.12 mL, 2.0 mmol) were added by syringe and vigorously stirred for 20 h at rt. Upon completion of the reaction, the contents of the flask were diluted with brine, and the mixture was extracted with EtOAc. The solution obtained was dried over anhydrous MgSO4, filtered, and concentrated by rotary evaporation. The residue was purified by flash chromatography eluting with hexane/EtOAc to afford the product.