Combined experimental and computational investigations of rhodium-catalysed C-H functionalisation of pyrazoles with alkenes

Chemistry - A European Journal

Volumn 21, Issue 7, 2015, Pages 3087-3096

  Algarra, Andrés G ^a   Davies, David L ^b   Khamker, Qudsia ^b   Macgregor, Stuart A ^a   McMullin, Claire L ^a   Singh, Kuldip ^b   Villa Marcos, Barbara ^b  

^a HERIOT WATT UNIVERSITY   (United Kingdom)

^b UNIVERSITY OF LEICESTER   (United Kingdom)

Author keywords

C H activation; Coupling reactions; Density functional calculations; Reaction mechanisms; Rhodium

Indexed keywords

ACTIVATION ANALYSIS; ADDITION REACTIONS; ALKENYLATION; CARBON DIOXIDE; CHEMICAL BONDS; CHEMICAL REACTIONS; COMPUTATION THEORY; HYDROCARBONS; KETONES; RHODIUM; STYRENE;

AZA-MICHAEL REACTION; C-H ACTIVATION; COMPUTATIONAL INVESTIGATION; COMPUTATIONAL STUDIES; COUPLING REACTION; METHYL VINYL KETONES; OXIDATIVE COUPLING PRODUCT; REACTION MECHANISM;

DENSITY FUNCTIONAL THEORY;

EID: 84921827334     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201405550     Document Type: Article

References (56)

1. a) L. Ackermann, Chem. Rev. 2011, 111, 1315;
2. b) D. Alberico, M. E. Scott, M. Lautens, Chem. Rev. 2007, 107, 174;
3. c) F. Bellina, R. Rossi, Chem. Rev. 2010, 110, 1082;
4. d) X. Chen, K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew. Chem. Int. Ed. 2009, 48, 5094;
5. Angew. Chem. 2009, 121, 5196;
6. e) D. A. Colby, R. G. Bergman, J. A. Ellman, Chem. Rev. 2010, 110, 624;
7. f) T. W. Lyons, M. S. Sanford, Chem. Rev. 2010, 110, 1147;
8. g) G. Song, F. Wang, X. Li, Chem. Soc. Rev. 2012, 41, 3651;
9. h) T. Satoh, M. Miura, Chem. Eur. J. 2010, 16, 11212;
10. i) L. Ackermann, Acc. Chem. Res. 2014, 47, 281.
11. a) D. L. Davies, S. M. A. Donald, O. Al-Duaij, J. Fawcett, C. Little, S. A. Macgregor, Organometallics 2006, 25, 5976;
12. b) D. L. Davies, S. M. A. Donald, O. Al-Duaij, S. A. Macgregor, M. Polleth, J. Am. Chem. Soc. 2006, 128, 4210;
13. c) D. L. Davies, S. M. A. Donald, S. A. Macgregor, J. Am. Chem. Soc. 2005, 127, 13754;
14. d) Y. Boutadla, D. L. Davies, S. A. Macgregor, A. I. Poblador-Bahamonde, Dalton Trans. 2009, 5820;
15. e) Y. Boutadla, D. L. Davies, S. A. Macgregor, A. I. Poblador-Bahamonde, Dalton Trans. 2009, 5887;
16. f) Y. Musashi, S. Sakaki, J. Am. Chem. Soc. 2000, 122, 3867;
17. g) D. García-Cuadrado, A. A. C. Braga, F. Maseras, A. M. Echavarren, J. Am. Chem. Soc. 2006, 128, 1066;
18. h) M. Lafrance, K. Fagnou, J. Am. Chem. Soc. 2006, 128, 16496;
19. i) M. Lafrance, C. N. Rowley, T. K. Woo, K. Fagnou, J. Am. Chem. Soc. 2006, 128, 8754;
20. j) S. I. Gorelsky, D. Lapointe, K. Fagnou, J. Am. Chem. Soc. 2008, 130, 10848;
21. k) L. Ackermann, R. Vicente, A. Althammer, Org. Lett. 2008, 10, 2299.
22. N. Guimond, C. Gouliaras, K. Fagnou, J. Am. Chem. Soc. 2010, 132, 6908.
23. S. Rakshit, C. Grohmann, T. Besset, F. Glorius, J. Am. Chem. Soc. 2011, 133, 2350.
24. a) Y. Boutadla, O. Al-Duaij, D. L. Davies, G. A. Griffith, K. Singh, Organometallics 2009, 28, 433;
25. b) Y. Boutadla, D. L. Davies, O. Al-Duaij, J. Fawcett, R. C. Jones, K. Singh, Dalton Trans. 2010, 39, 10447;
26. c) Y. Boutadla, D. L. Davies, R. C. Jones, K. Singh, Chem. Eur. J. 2011, 17, 3438;
27. d) K. J. T. Carr, S. A. Macgregor, D. L. Davies, K. Singh, B. Villa-Marcos, Chem. Sci. 2014, 5, 2340;
28. e) D. L. Davies, O. Al-Duaij, J. Fawcett, M. Giardiello, S. T. Hilton, D. R. Russell, Dalton Trans. 2003, 4132;
29. f) L. Li, W. W. Brennessel, W. D. Jones, Organometallics 2009, 28, 3492;
30. g) L. Li, Y. Jiao, W. W. Brennessel, W. D. Jones, Organometallics 2010, 29, 4593;
31. h) J. B. Sortais, N. Pannetier, A. Holuigue, L. Barloy, C. Sirlin, M. Pfeffer, N. Kyritsakas, Organometallics 2007, 26, 1856;
32. i) N. Wang, B. Li, H. Song, S. Xu, B. Wang, Chem. Eur. J. 2013, 19, 358.
33. A. G. Algarra, W. B. Cross, D. L. Davies, Q. Khamker, S. A. Macgregor, C. L. McMullin, K. Singh, J. Org. Chem. 2014, 79, 1954.
34. a) N. Guimond, S. I. Gorelsky, K. Fagnou, J. Am. Chem. Soc. 2011, 133, 6449;
35. b) N. Quiñones, A. Seoane, R. Garcia-Fandino, J. L. Mascarenas, M. Gulias, Chem. Sci. 2013, 4, 2874.
36. a) Q. Zhang, H.-Z. Yu, Y.-T. Li, L. Liu, Y. Huang, Y. Fu, Dalton Trans. 2013, 42, 4175;
37. b) L. Xu, Q. Zhu, G. Huang, B. Cheng, Y. Xia, J. Org. Chem. 2012, 77, 3017.
38. N. Umeda, K. Hirano, T. Satoh, M. Miura, J. Org. Chem. 2009, 74, 7094.
39. a) A. M. Martínez, N. Rodriguez, R. Gomez Arrayas, J. C. Carretero, Chem. Commun. 2014, 50, 6105;
40. b) X. Wei, F. Wang, G. Song, Z. Du, X. Li, Org. Biomol. Chem. 2012, 10, 5521.
41. X. Li, M. Zhao, J. Org. Chem. 2011, 76, 8530.
42. The free NH pyrazoles can exist as a mixture of tautomers. Only one tautomer can undergo NH and CH activation, that with the NH group next to the phenyl. In all the schemes only this tautomer is drawn, however, the other tautomer is also likely to be present in solution.
43. The strongest ions in the ESI mass spectrum are those of the free vinyl pyrazole, however, on close inspection, a low intensity peak was observed that corresponds to the copper dimer 2aa. By using an ASAP probe, the ions of the dimer were much more intense.
44. a) M. Munakata, S. Kitagawa, S. Kosome, A. Asahara, Inorg. Chem. 1986, 25, 2622;
45. b) H. V. R. Dias, S. A. Richey, H. V. K. Diyabalanage, J. Thankamani, J. Organomet. Chem. 2005, 690, 1913;
46. c) J. J. Allen, A. R. Barron, Dalton Trans. 2011, 40, 1189;
47. d) R. G. Salomon, J. K. Kochi, J. Organomet. Chem. 1974, 64, 135.
48. In some cases, depending on the time taken for the extraction, not all of 2aa was converted into 3aa.
49. The yields shown are the best for a particular product but they did show some variation from one reaction to another. In addition, separation of the products by column chromatography was particularly difficult and so some mixed fractions were discarded. The actual yield in any given run could therefore vary by up to 10%.
50. The yields of isolated product are quite different to the crude yield, in this case possibly due to losses on the column.
51. The values reported here include the correction for basis-set effects with BS2 and so differ slightly from those previously reported. A comparison of results obtained with each basis set is given in Table S1 in the Supporting Information.
52. -1 and so is uncompetitive with insertion into the Rh-aryl bond.
53. trans (see Figure S2 in the Supporting Information).
54. -1.
55. 2,1 shown in Figure 7, see Figure S3 in the Supporting Information.
56. R. J. Deeth, A. Smith, J. M. Brown, J. Am. Chem. Soc. 2004, 126, 7144.