Copper-mediated chelation-assisted ortho nitration of (hetero)arenes

Organic Letters

Volumn 13, Issue 24, 2011, Pages 6536-6539

  Zhang, Lin ^a   Liu, Zhenhua ^a   Li, Huiqin ^a   Fang, Guichun ^a   Barry, Badru Deen ^a   Belay, Tuemay Abadi ^a   Bi, Xihe ^a,b   Liu, Qun ^a  

^a NORTHEAST NORMAL UNIVERSITY   (China)

^b DALIAN UNIVERSITY OF TECHNOLOGY   (China)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 84055223634     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol2028288     Document Type: Article

References (23)

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4. For a leading review on "chelation-directed C-H functionalization", see: Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147.
5. Liu, Y.-K.; Lou, S.-J.; Xu, D.-Q.; Xu, Z.-Y. Chem.; Eur. J. 2010, 16, 13590.
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9. 1, 2, 3-TCP may act as an oxidant or proton donor like other chlorinated alkanes: (a) Jin, L.; Xin, J.; Huang, Z.; He, J.; Lei, A. J. Am. Chem. Soc. 2010, 132, 9607.
10. (b) Ilies, L.; Asako, S.; Nakamura, E. J. Am. Chem. Soc. 2011, 133, 7672.
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12. For a review on "kinetic isotope effects in the study of organometallic reaction mechanisms", see: (a) Gómez-Gallego, M.; Sierra, M. A. Chem. Rev. 2011, 111, 4857.
13. Large KIE values have been reported in C-H hydroxylations catalyzed by bis(μ -oxo)dicopper or bis(μ -oxo)-diiron complexes, in which a free radical mechanism was proposed; see; (b) Kim, C.; Dong, Y.; Que, L., Jr. J. Am. Chem. Soc. 1997, 119, 3635.
14. A small secondary reverse isotope effect was often observed in electrophilic aromatic nitration; see: Olah, G. A.; Kuhn, S. J.; Flood, S. H. J. Am. Chem. Soc. 1961, 83, 4571.
15. Olah, G. A.; Laali, K. K.; Sandford, G. Proc. Nati. Acad. Sci. U.S.A. 1992, 89, 6670.
16. 2O released nitrogen dioxide at a lower temperature (ca. 200 °C)
17. see: Morozov, I. V.; Znamenkov, K. O.; Korenev, Y. M.; Shlyakhtin, O. A. Thermochim. Acta 2003, 403, 173.
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19. Note that the nitration of 1a1 under the optimal reaction conditions (Table 1, entry 3) was slightly retarded in the presence of KOAc (50 mol %). The added acetate ion is assumed to prevent the anion exchange with nitrate ion.
20. A four-centered transition state was proposed to account for observed large KIEs; see: Wayland, B. B.; Ba, S.; Sherry, A. E. J. Am. Chem. Soc. 1991, 113, 5305.
21. For a related mechanistic speculation that phenol was nitrated by · NO2 produced from the decomposition of an iron peroxynitrite complex, see: (a) Tran, N. G.; Kalyvas, H.; Skodje, K. M.; Hayashi, T.; Moënne-Loccoz, P.; Callan, P. E.; Shearer, J.; Kirschenbaum, L. J.; Kim, E. J. Am. Chem. Soc. 2011, 133, 1184.
22. For a report that nitration of phenols with gaseous nitrogen dioxide, see; (b) Astolfi, P.; Panagiotaki, M.; Greci, L. Eur. J. Org. Chem. 2005, 3052.
23. For examples of C-H bond activation with possible linear fourcentered transition state, see: Cui, W.; Wayland, B. B. J. Am. Chem. Soc. 2004, 126, 8266