Mechanistic insight into direct arylations with ruthenium(II) carboxylate catalysts

Organic Letters

Volumn 12, Issue 21, 2010, Pages 5032-5035

  Ackermann, Lutz ^a   Vicente, Rubén ^a   Potukuchi, Harish K ^a   Pirovano, Valentina ^a  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 78049501131     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol102187e     Document Type: Article

References (51)

1. Selected recent reviews
2. Colby, D. A.; Bergman, R. G.; Ellman, J. A. Chem. Rev. 2010, 110, 624-655
3. Ackermann, L.; Vicente, R.; Kapdi, A. Angew. Chem., Int. Ed 2009, 48, 9792-9826
4. Thansandote, P.; Lautens, M. Chem.-Eur. J. 2009, 15, 5874-5883
5. Kakiuchi, F.; Kochi, T. Synthesis 2008, 3013-3039
6. Ackermann, L. Synlett 2007, 507-526
7. Satoh, T.; Miura, M. Chem. Lett. 2007, 36, 200-205
8. Ackermann, L. Modern Arylation Methods; Wiley-VCH: Weinheim, Germany, 2009.
9. For selected recent examples of ruthenium-catalyzed direct arylations with aryl bromides, see
10. Oi, S.; Sasamoto, H.; Funayama, R.; Inoue, Y. Chem. Lett. 2008, 37, 994-995
11. Ackermann, L.; Althammer, A.; Born, R. Tetrahedron 2008, 64, 6115-6124
12. Oi, S.; Funayama, R.; Hattori, T.; Inoue, Y. Tetrahedron 2008, 64, 6051-6059
13. Ackermann, L.; Althammer, A.; Born, R. Synlett 2007, 2833-2836 and references cited therein
14. For select recent examples of ruthenium-catalyzed direct arylations with boron-based arylating reagents, see
15. Kitazawa, K.; Kochi, T.; Sato, M.; Kakiuchi, F. Org. Lett. 2009, 11, 1951-1954
16. Park, Y. J.; Jo, E.-A.; Jun, C.-H. Chem. Commun. 2005, 1185-1187 and references cited therein
17. A review: Ackermann, L.; Vicente, R. Top. Curr. Chem. 2010, 292, 211-229
18. Representative examples: ArOTs
19. Ackermann, L.; Althammer, A.; Born, R. Angew. Chem., Int. Ed. 2006, 45, 2619-2622 ArCl: Ackermann, L.; Born, R.; Álvarez-Bercedo, P. Angew. Chem., Int. Ed. 2007, 46, 6364-6367
20. Pozgan, F.; Dixneuf, P. H. Adv. Synth. Catal. 2009, 351, 1737-1743
21. Ackermann, L.; Born, R.; Vicente, R. ChemSusChem 2009, 2, 546-549
22. 2O: Ackermann, L. Org. Lett. 2005, 7, 3123-3125
23. Grounds, H.; Anderson, J. C.; Hayter, B.; Blake, A. J. Organometallics 2009, 28, 5289-5292
24. Luo, N.; Yu, Z. Chem.-Eur. J. 2010, 16, 787-791
25. Oi, S.; Sakai, K.; Inoue, Y. Org. Lett. 2005, 7, 4009-4011
26. Oi, S.; Fukita, S.; Hirata, N.; Watanuki, N.; Miyano, S.; Inoue, Y. Org. Lett. 2001, 3, 2579-2581
27. Özdemir, I.; Demir, S.; Cetinkaya, B.; Gourlaouen, C.; Maseras, F.; Bruneau, C.; Dixneuf, P. H. J. Am. Chem. Soc. 2008, 130, 1156-1157 See also: Davies, D. L.; Donald, S. M. A.; Macgregor, S. A. J. Am. Chem. Soc. 2005, 127, 13754-13755
28. Boutadla, Y.; Davies, D. L.; Macgregor, S. A.; Poblador-Bahamonde, A. I. Dalton Trans. 2009, 5820-5831
29. Ackermann, L.; Vicente, R.; Althammer, A. Org. Lett. 2008, 10, 2299-2302
30. For examples of applications to direct arylations, see
31. Ackermann, L.; Novák, P.; Vicente, R.; Pirovano, V.; Potukuchi, H. K. Synthesis 2010, 2245-2253
32. Ackermann, L.; Vicente, R. Org. Lett. 2009, 11, 4922-4925
33. Ackermann, L.; Mulzer, M. Org. Lett. 2008, 10, 5043-5045
34. Ackermann, L. Pure Appl. Chem. 2010, 82, 1403-1413
35. For direct alkylations, see: Ackermann, L.; Novak, P.; Vicente, R.; Hofmann, N. Angew. Chem., Int. Ed. 2009, 48, 6045 - 6048.
36. Ackermann, L.; Novák, P. Org. Lett. 2009, 11, 4966-4969
37. Ackermann, L. Chem. Commun. 2010, 46, 4866-4877
38. The crystal structure of complex 3 has been deposited at the Cambridge Crystallographic Data Centre (CCDC-757573).
39. Mechanistic studies in NMP as solvent are hampered among others by its potential competitive coordination to ruthenium complexes, which in our hands results in catalytic reactions with lower robustness.
40. 3 or KOAc as base, respectively (see also Table S-1 in the Supporting Information).
41. Shen, K.; Fu, Y.; Li, J.-N.; Liu, L.; Guo, Q.-X. Tetrahedron 2007, 63, 1568-1576
42. Clot, E.; Mégret, C.; Eisenstein, O.; Perutz, R. N. J. Am. Chem. Soc. 2009, 131, 7817-7827
43. Generally, the following order in reactivity is observed in ruthenium-catalyzed direct arylations: ArBr > ArCl > ArOTs. For the synthesis of a cyclometalated complex, see
44. Fernandez, S.; Pfeffer, M.; Ritleng, V.; Sirlin, C. Organometallics 1999, 18, 2390-2394 See also ref 5.
45. For previous studies on the reversibility of ruthenium-catalyzed C-H bond cleavage/C-C bond formation reactions, see
46. Kozhushkov, S. I.; Yufit, D. S.; Ackermann, L. Org. Lett. 2008, 10, 3409-3412 and references cited therein
47. During the preparation of this manuscript a study on ruthenium-catalyzed C-H bond functionalizations in NMP as solvent was reported
48. Prades, A.; Poyatos, M.; Peris, E. Adv. Synth. Catal. 2010, 352, 1155-1162
49. Addition of 1 equiv of 2,6-di- tert -butyl- p -cresol or catalytic amounts of galvinoxyl did not affect the outcome of representative ruthenium-catalyzed direct arylations with aryl chlorides 5. However, lower yields were obtained when employing 1 equiv of galvinoxyl or of TEMPO. For reactions of radical traps with transition metal hydrides, see for example
50. Albéniz, A. C.; Espinet, P.; López-Fernández, R.; Den, A. J. Am. Chem. Soc. 2002, 124, 11278-11279
51. Intermolecular competition experiments between differently substituted arenes 4 indicate the oxidative addition, rather than the reductive elimination to be rate determining (see Scheme 7, and Scheme S-1 in the Supporting Information).