Activation of allylic C-F bonds: Palladium-catalyzed allylic amimation of 3,3-difluoropropenes

Angewandte Chemie - International Edition

Volumn 49, Issue 6, 2010, Pages 1123-1127

  Pigeon, Xavier ^a   Bergeron, Maxime ^a   Barabé, Francis ^b   Dubé, Pascal ^b   Frost, Heather N ^b   Paquin, Jean François ^a  

^a UNIVERSITÉ LAVAL   (Canada)

^b PFIZER INC   (United States)

Author keywords

Amination; C F activation; Fluoroalkenes; Homogeneous catalysis; Palladium

Indexed keywords

AMIMATION; C-F ACTIVATION; C-F BONDS; CHEMICAL EQUATIONS; FLUOROALKENES; HOMOGENEOUS CATALYSIS;

AMINES; CATALYSIS; CHEMICAL BONDS; REACTION KINETICS;

PALLADIUM;

ALKENE; ALLYL COMPOUND; CARBON; FLUORINE; FLUOROCARBON; PALLADIUM; PROPYLENE;

AMINATION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY;

ALKENES; ALLYL COMPOUNDS; AMINATION; CARBON; CATALYSIS; FLUORINE; FLUOROCARBONS; MOLECULAR STRUCTURE; PALLADIUM;

EID: 76249094924     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.200904747     Document Type: Article

References (66)

1. For selected reviews on C-F bond activation using transition metals, see : a) J. L. Kiplinger, T. G. Richmond, C. E. Ostenberg, Chem. Rev. 1994, 94, 373-431;
2. b) T. Braun, R. N. Perutz, Chem. Commun. 2002, 2749-2757;
3. c) U. Mazurek, H. Schwarz, Chem. Commun. 2003, 1321-1326;
4. d) H. Torrens, Coord Chem. Rev. 2005, 249, 1957-1985;
5. e) H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119-2183;
6. f) G. Meier, M. Braun, Angew. Chem. 2009, 121, 1575-1577;
7. Angew. Chem. Int. Ed. 2009, 48, 1546-1548.
8. a) M. Hudlicky, J. Fluorine Chem. 1989, 44, 345-359;s
9. b)L. Hintermann, F. Läng, P. Maire, A. Togni, Eur. J. Inorg. Chem. 2006, 1397-1412;
10. c) J. Ichikawa, R. Nadano, N. Ito, Chem. Commun. 2006, 4425-4427;
11. d)T. Narumi, K. Tomita, E. Inokuchi, K. Kobayashi, S. Oishi, H. Ohno, N. Fujii, Org. Lett. 2007, 9, 3465-3468;
12. e) A. Hazari, V. Gouverneur, J. M. Brown, Angew. Chem. 2009, 121, 1322-1325;
13. Angew. Chem. Int. Ed. 2009,48,1296-1299.
14. For selected books, reviews, or accounts, see: a) T. Hiyama in Organofluorine Compounds; Chemistry and Applications (Ed.: H. Yamamoto), Springer, Berlin, 2000 and the references therein;
15. b)B. E. Smart, J. Fluorine Chem. 2001, 109, 3-11;
16. c) J.-A. Ma, D. Cahard, Chem. Rev. 2004, 104, 6119-6146;
17. d) M. Shimizu, T. Hiyama, Angew. Chem. 2005, 117,218-234;
18. Angew. Chem. Int. Ed. 2005, 44, 214-231;
19. e) A. M. Thayer, Chem. Eng. News 2006, 84, 15 -24;
20. f) K. L. Kirk, J. Fluorine Chem. 2006, 127, 1013-1029;
21. g) J.-P. Bégué, D. Bonnet-Delpon, J. Fluorine Chem. 2006,727,992-1012 ;
22. h) G. K. S. Prakash, J. Hu, Acc. Chem. Res 2007, 40, 921-930;
23. i) K. Müller, C. Faeh, F. Diederich, Science 2007, 317, 1881-1886;
24. j) S. Purser, P. R. Moore, S. Swallow, V Gouverneur, Chem. Soc. Rev. 2008, 37, 320-330;
25. k)W. K. Hagmann, J. Med. Chem. 2008, 51, 4359-4369;
26. J.-A. Ma, D. Cahard, Chem. Rev. 2008, 108, PR1-PR43.
27. For our own. work in this area, see : a) É. Bélanger, K. Cantin, O. Messe, M. Tremblay, J-F. Paquin, J. Am. Chem. Soc 2007, 129, 1034-1125;
28. b) É. Bélanger, C. Houzé, N. Guimond, K. Cantin, J-F. Paquin, Chem. Commun. 2008, 3251-3253;
29. c) G. Landelle, P. A. Champagne, X. Barbeau, J-F. Paquin, Org. Lett. 2009, 11, 681-684;
30. d) G. Landelle, M.-O. Turcotte-Savard, X Marterer, P. A. Champagne, J-F. Paquin, Org. Lett. 2009, 11, 5406-5409.
31. Herein, the term "oxidative addition" is used broadly to define the insertion of a metal complex into a covalent bond, formally involving an overall two-electron loss at the metal. However, a more rigorous term would be to describe this transformation as an "electrophilic addition", as the mechanism, most likely proceeds by a nucleophilic substitution pathway where the leaving group is not bound to the metal. See R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, 4th ed., Wiley, Hoboken, 2005.
32. A palladium-catalyzed hydride reduction of 3,3-difluoropropenes was published during the course of our studies; see Ref. [2d].
33. For example, see: a) S. Hara in Fluorine-Containing Synthons (Ed.: V A. Soloshonok), American Chemical Society, Washington, 2005, pp. 121-172, and the references therein (ACS Symposium Series 911);
34. b) G Dutheuil, S. Couve-Bonnaire, X. Pannecoucke, Angew. Chem. 2007, 119, 1312-1314;
35. Angew. Chem. Int. Ed. 2007, 46, 1290-1292.
36. For example, see : a) L. G Boros, B. De Corte, R. H. Gimi, J. T. Welch, Y Wu, R. E. Handschumacher, Tetrahedron Lett. 1994, 35, 6033-6036;
37. b) P. A. Bartlett, A. Otake, J. Org. Chem. 1995, 60, 3107-3111;
38. c) R. X Sciotti, M. Pliushchev, P. E. Wiedeman, D. Balli, R. Flamm, A. M. Nilius, K. Marsh, D. Stolarik, R. Jolly, R. Ulrich, S. W Djuric, Bioorg. Med. Chem. Lett 2002,72,2121-2123;
39. d) P. Van der Veken, K. Senten, I. Kertèsz, I. De Meester, A.-M. Lambeir, M.-B. Maes, S. Scharpé, A. Haemers, K. Augustyns, J. Med. Chem. 2005, 48, 1768-1780;
40. e) T. Deng, S. Shan, Z.-B. Li, Z.-W Wu, C-Z. Liao, B. Ko, X.-P. Lu, X Cheng, Z.-Q. Ning, Biol Pharm. Bull. 2005, 28, 1192-1196;
41. f) A. Niida, K. Tomita, M. Mizumoto, H. Tanigaki, T. Terada, S. Oishi, A. Otaka, K.-i. Inui, N. Fuji, Org. Lett. 2006,8, 613-616;
42. g) D. Alloatti, G. Giannini, W. Cabri, I. Lustrati, M. Marzi, A. Ciacci, G. Gallo, M. O. Tinti, M. Marcellini, T. Riccioni, M. B. Guglielmi, P. Carminati, C. Pisano, J. Med. Chem. 2008, 51, 2708-2721.
43. For recent examples, see: a) F. Babudri, G M. Farinola, F. Naso, R. Ragni, Chem. Commun. 2007,1003-1022;
44. b) F. Babudri, A. Cardone, G M. Farinola, C. Martinelli, R. Mendichi, F. Naso, M. Striccoli, Eur. J. Org. Chem. 2008, 1977-1982.
45. Compound 1 was synthesized using a simple three-step process that could be performed on a multi-gram, scale; see the Supporting Information for experimental, details.
46. a) N. P. Buu-Hoï V. Q. Yen, N. D. Xuong, J. Org. Chem. 1958, 23, 189-190;
47. b) K. K. Laali, G. I. Borodkin, J. Chem. Soc. Perkin Trans 2 2002, 953-957.
48. Other solvents, such as tetrahydrofuran, toluene, and N, Ndimethylformamide, may be used with similar results.
49. Aniline derivatives (aniline, N-methylaniline, 1, 2, 3, 4-tetrahydroquinoline) are unreactive under these conditions.
50. M. Kirihara, T. Takuwa, S. Takizawa, T. Momose, H. Nemoto, Tetrahedron 2000, 56, 8275-8280.
51. a) A. Pfaltz, M. Lautens in Comprehensive Asymmetric Catalysis, Vol.2 (Eds.: E.N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999, pp. 833-884, and the references therein;
52. b) J.-F. Paquin, M. Lautens in Comprehensive Asymmetric Catalysis, supplement No. 2. (Eds.: E.N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 2004, pp. 73-95 and the references therein.
53. I. D. G. Watson, A. K. Yudin, J. Am. Chem. Soc. 2005, 727, 17516-17529.
54. U. Burckhardt, M. Baumann, A. Togni, Tetrahedron: Asymmetry 1997, 8, 155-159.
55. 1 -σ Complex, see: a) C. Amatore, A. Jutand, M. A. M'Barki, G. Meyer, L. Mottier, Eur. J. Inorg. Chem 2001, 873-880;
56. b)T. Cantat, E. Génin, C. Giroud, G. Meyer, A. Jutand, J. Organomet. Chem. 2003, 657, 365-376. Studies to determine the exact nature of palladium complex 14 are underway.
57. The fluoride counter ion in complex 14 is unlikely to be "naked" and is presumably stabilized by hydrogen bonding with an amine, HF produced in the reaction and/or adventitious water. The exact nature of the fluoride ion. is not known, at present.
58. II-F see: D. A. Watson, M. Su, G. Teverovskiy, Y. Zhang, J. García-Fortanet, T. Kinzel, S. L. Buchwald, Science 2009, 325, 1661-1664.
59. a) J. Tsuji, I. Minami, I. Shimizu, Tetrahedron Lett. 1983, 24, 1793-1796;
60. b)J. Tsuji, I. Shimizu, I. Minami, Y. Ohashi, T. Sugiura, K. Takahashi, J. Org. Chem. 1985, 50, 1523-1529;
61. c) J. Tsuji, I. Minami, Acc Chem. Res. 1987, 20,140-145.
62. a) E. Keinan, Z. Roth, J. Org. Chem. 1983, 48,1772-1774;
63. b) E. Keinan, M. Peretz, J. Org. Chem. 1983, 48, 5302-5309;
64. c) T. Konno, K. Nagata, T. Ishihara, H. Yamanaka, J. Org. Chem. 2002, 67, 1768-1775.
65. Alternatively, the preference for the attack at Cl might be explained by a higher density of positive charge at the carbon of the πallyl palladium, caused by the strongly electron-withdrawing fluorine atom; see: J. Xu, X.-L. Qiu, F.-L. Qing, Beilstein J. Org. Chem. 2008, 4, No.18.
66. 19 NMR spectroscopy following heating 1 with morpholine (2.5 equiv) in acetonitrile at 70° C for 16 h.