Generation of iminyl copper species from α-azido carbonyl compounds and their catalytic C-C bond cleavage under an oxygen atmosphere

Organic Letters

Volumn 12, Issue 9, 2010, Pages 2052-2055

  Chiba, Shunsuke ^a   Zhang, Line ^a   Ang, Gim Yean ^a   Hui, Benjamin Wei Qiang ^a  

^a Nanyang Technological University   (Singapore)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 77951836519     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol100522z     Document Type: Article

References (44)

1. For recent reviews, see
2. Satoh, T.; Miura, M. Top. Organomet. Chem. 2005, 14, 1
3. Jun, C.-H. Chem. Soc. Rev. 2004, 33, 610
4. Rybtchinski, B.; Milstein, D. Angew. Chem., Int. Ed. 1999, 38, 870
5. Murakami, M.; Ito, Y. In Activation of Unreactive Bonds and Organic Synthesis; Murai, S., Ed.; Springer: New York, 1999; pp 97-129.
6. Zhao, P.; Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 11618
7. Nishimura, T.; Uemura, S. J. Am. Chem. Soc. 2000, 122, 12049
8. For generation of iminyl metal species and their application, see
9. Chiba, S.; Xu, Y.-J.; Wang, Y.-F. J. Am. Chem. Soc. 2009, 131, 12886
10. Wang, Y.-F.; Chiba, S. J. Am. Chem. Soc. 2009, 131, 12570
11. Gerfaund, T.; Neuville, L.; Zhu, J. Angew. Chem., Int. Ed. 2009, 48, 572
12. Liu, S.; Liebeskind, L. S. J. Am. Chem. Soc. 2008, 130, 6918
13. Wang, Y.-F.; Toh, K. K.; Chiba, S.; Narasaka, K. Org. Lett. 2008, 10, 5019
14. Brasche, G.; Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47, 1932
15. Ichikawa, J.; Nadano, R.; Ito, N. Chem. Commun. 2006, 4423
16. Narasaka, K.; Kitamura, M. Eur. J. Org. Chem. 2005, 4505
17. For recent selected reports on synthesis of nitriles
18. Zhou, W.; Zhang, L.; Jiao, N. Angew. Chem., Int. Ed. 2009, 48, 7094
19. Oishi, T.; Yamaguchi, K.; Mizuno, N. Angew. Chem., Int. Ed. 2009, 48, 6286
20. Kangani, C. O.; Day, B. W.; Kelley, D. E. Tetrahedron Lett. 2008, 49, 914
21. Yamaguchi, K.; Fujiwara, H.; Ogasawara, Y.; Kotani, M.; Mizuno, N. Angew. Chem., Int. Ed. 2007, 46, 3922
22. Kuo, C.-W.; Zhu, J.-L.; Wu, J.-D.; Chu, C.-M.; Yao, C.-F.; Shia, K.-S. Chem. Commun. 2007, 301
23. Iida, S.; Togo, H. Tetrahedron 2007, 63, 8274
24. Schareina, T.; Zapf, A.; Beller, M. Chem. Commun. 2004, 1388
25. Zanon, J.; Klapars, A.; Buchwald, S. L. J. Am. Chem. Soc. 2003, 125, 2890
26. Ishihara, K.; Furuya, Y.; Yamamoto, H. Angew. Chem., Int. Ed. 2002, 41, 2983
27. Choi, E.; Lee, C.; Na, Y.; Chang, S. Org. Lett. 2002, 4, 2369
28. Hernández, R.; Léon, E. I.; Moreno, P.; Suárez, E. J. Org. Chem. 1997, 62, 8974
29. Hui, B. W.-Q.; Chiba, S. Org. Lett. 2009, 11, 729
30. For radical fragmentation of α-aminocarbonyliminyl radicals, see: Bencivenni, G.; Lanza, T.; Leardini, R.; Minozzi, M.; Nanni, D.; Spagnolo, P.; Zanardi, G. J. Org. Chem. 2008, 73, 4721
31. For examples of C-C bond cleavage with elimination of a carbonyl moiety, see
32. Ram, R. N.; Singh, L. Tetrahedron Lett. 1995, 36, 5401
33. Jin, S.-J.; Arora, P. K.; Sayre, L. M. J. Org. Chem. 1990, 55, 3011
34. For a report on the coordination of the internal nitrogen of azido moiety with a Cu(II) complex, see: Barz, M.; Herdweck, E.; Thiel, W. R. Angew. Chem., Int. Ed. 1998, 37, 2262
35. For proposed mechanisms on the formation of phenanthridine 5, see the Supporting Information.
36. 2, see
37. Kim, S.; Lee, J. I. J. Chem. Soc., Chem. Commun. 1981, 1231
38. van Koten, G.; Noltes, J. G. J. Chem. Soc., Chem. Commun. 1972, 59
39. For the chemical reactivity of acylperoxy metals, see
40. Cornell, C. N.; Sigman, M. S. In Activation of Small Molecules; Tolman, W. B., Ed.; Wiely: Weinheim, 2006; pp 159-186 and references therein.
41. It was confirmed that the reaction of styrene (12) under the present catalytic conditions without azide 10 did not form styrene oxide (13) at all.
42. For generation of iminyl lithium species from α-azido carbonyl compounds, see: Manis, P. A.; Rathke, M. W. J. Org. Chem. 1980, 45, 4952
43. For iminyl titanium(IV) species, see: Ciez, D. Org. Lett. 2009, 11, 4282
44. The stoichiometric reactions under an Ar atmosphere (Table 1, entry 1 and Scheme 5 b) indicated that iminyl copper(II) II could form nitrile 3 and acylcopper VI by β-carbon elimination (path A). Based on these results, it was speculated as another mechanistic possibility (path B) that peroxycopper III undergoes β-fission to lead formation of nitrile 3 and acylcopper VII, which isomerizes to acylperoxy copper IV.