Catalytic intermolecular amination of C-H bonds: Method development and mechanistic insights

Journal of the American Chemical Society

Volumn 129, Issue 3, 2007, Pages 562-568

  Fiori, Kristin Williams ^a   Du Bois, J ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINATION; CATALYSIS; OXIDATION; REACTION KINETICS; SUBSTITUTION REACTIONS;

C-H BONDS; CHEMOSELECTIVITY; INTERMOLECULAR AMINATION; MECHANISTIC INSIGHTS;

CHEMICAL BONDS;

BENZILIC ACID; CARBON; HYDROGEN; NITROGEN 15;

AMINATION; ARTICLE; BINDING AFFINITY; CATALYSIS; CHEMICAL BINDING; HYDROGEN BOND; MOLECULAR DYNAMICS; MOLECULAR MECHANICS; REACTION ANALYSIS; REACTION OPTIMIZATION;

ALKANES; AMINES; AMINO ALCOHOLS; BENZENE DERIVATIVES; CARBON; CATALYSIS; DIAMINES; HYDROGEN; NITROGEN ISOTOPES; OXIDATION-REDUCTION; SPECTROPHOTOMETRY, ULTRAVIOLET;

EID: 33846430525     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0650450     Document Type: Article

References (61)

1. (a) Espino, C. G.; Du Bois, J. In Modern Rhodium-Catalyzed Organic Reactions; Evans, P. A., Ed.; Wiley-VCH: Weinheim, 2005; pp 379-416.
2. (b) Davies, H. M. L. Angew. Chem., Int. Ed. 2006, 45, 6422-6425.
3. (c) Lebel, H.; Leogane, O.; Huard, K.; Lectard, S. Pure Appl. Chem. 2006, 78, 363-375.
4. (d) Halfen, J. A. Curr. Org. Chem. 2005, 9, 657-669.
5. (e) Müller, P.; Fruit, C. Chem. Rev. 2003, 103, 2905-2919.
6. (f) Dauban, P.; Dodd, R. H. Synlett 2003, 1571-1586.
7. For some recent examples, see: (a) Fraunhoffer, K. J.; Prabagaran, N.; Sirois, L. E.; White, M. C. J. Am Chem. Soc. 2006, 128, 9032-9033.
8. (b) Giri, R.; Liang, J.; Lei, J.-G.; Li, J.-J.; Wang, D.-H.; Chen, X.; Naggar, I. C.; Guo, C.; Foxman, B. M.; Yu, J.-Q. Angew. Chem., Int. Ed. 2005, 44, 7420-7424.
9. (c) Desai, L. V.; Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 9542-9543.
10. (d) Wong, M.-K.; Chung, N.-W.; He, L.; Yang, D. J. Am. Chem. Soc. 2003, 125, 158-162.
11. (e) Dangel, B. D.; Johnson, J. A.; Sames, D. J. Am. Chem. Soc. 2001, 123, 8149-8150.
12. For representative examples of intermolecular C-H amination, see: (a) Fruit, C.; Müller, P. Tetrahedron: Asymmetry 2004, 15, 1019-1026.
13. (b) Díaz-Requejo, M. M.; Belderraín, T. R.; Nicasio, M. C.; Trofimenko, S.; Pérez, P. J. J. Am. Chem. Soc. 2003, 125, 12078-12079.
14. (c) Yamawaki, M.; Tsutsui, H.; Kitagaki, S.; Anada, M.; Hashimoto, S. Tetrahedron Lett. 2002, 43, 9561-9564.
15. (d) Liang, J.-L.; Yuan, S.-X.; Chan, P. W. H.; Che, C.-M. Org. Lett. 2002, 4, 4507-4510.
16. (e) Yu, X.-Q.; Huang, J.-S.; Zhou, X.-G.; Che, C.-M. Org. Lett. 2000, 2, 2233-2236.
17. (f) Yang, J.; Weinberg, R.; Breslow, R. Chem. Commun. 2000, 531-532.
18. Espino, C. G.; Fiori, K. W.; Kim, M.; Du Bois, J. J. Am. Chem. Soc. 2004, 126, 15378-15379.
19. 2 catalysis using limiting amounts of the starting hydrocarbon, see: Liang, C.; Robert-Peillard, F.; Fruit, C.; Müller, P.; Dodd, R. H.; Dauban, P. Angew. Chem., Int. Ed. 2006, 45, 4641-4644.
20. While this manuscript was in submission, Reddy and Davies reported enantioselective intermolecular C-H insertion reactions using a dirhodium catalyst derived from adamantyl S-glycine, see: Reddy, R. P.; Davies, H. M. L. Org. Lett. 2006, 8, 5013-5016.
21. Du Bois, J. Chemtracts: Org. Chem. 2005, 18, 1-13.
22. A 1-hour dropwise addition reduced product yields by ∼15%.
23. 2 in a single step; see Supporting Information for details. Stang, P. J.; Boehshar, M.; Wingert, H.; Kitamura, T. J. Am. Chem. Soc. 1988, 110, 3272-3278.
24. 2 was first employed for alkene aziridination reactions, see: Guthikonda, K.; Du Bois, J. J. Am. Chem. Soc. 2002, 124, 13672-13673.
25. 2 were measured in intramolecular C-H amination experiments, the details of which will appear in a forthcoming article: Fiori, K. W.; Espino, C. G.; Brodsky, B. H.; Du Bois, J., manuscript in preparation.
26. 2 as the nitrogen source, reaction yields are greatly diminished (< 10%) from those reported in Tables 1-3.
27. 2, see ref 6.
28. 2 = bis-{1,3-[N,N′-di(2, 4,6-triisopropylbenzenesulfonyl)-(2S,2′S),(5R, 5′R)-prolinate]benzene} dirhodium. Davies has reported the design and reactivity of this bridging prolinate complex. For leading references, see: (a) Davies, H. M. L.; Lee, G. H. Org. Lett. 2004, 6, 2117-2120.
29. (b) Davies, H. M. L.; Venkataramani, C. Org. Lett. 2003, 5, 1403-1406.
30. 2.
31. Reports by Che and Müller, Dauban, and Dodd also describe amination reactions using limiting amounts of substrate, see refs 3e and 5, respectively.
32. Isolable amounts (15-20%) of the C1/C4-diaminated products are also generated.
33. See Supporting Information for details.
34. 2N=IPh have found extensive use as nitrene equivalents, particularly for metal-catalyzed alkene aziridination reactions, see ref 1.
35. 2 using KOH, see: Liang, J.-L.; Yuan, S.-X.; Huang, J.-S.; Che, C.-M. J. Org. Chem. 2004, 69, 3610-3619.
36. Assignment is based on comparison of the NMR spectrum to that of authentic TcesN=IPh.
37. tBu). Such data are consistent with carboxylate dissociation and iodonium ion formation. Details of these experiments will be reported shortly.
38. Our observed trends in C-H bond reactivity parallel those observed for Rh-catalyzed diazoalkane insertion reactions. For leading references, see: (a) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds: From Cyclopropanes to Ylides; Wiley and Sons, Ltd.: New York, 1998.
39. (b) Davies, H. M. L.; Beckwith, R. E. J. Chem. Rev. 2003, 103, 2861-2903.
40. Also see: Davies, H. M. L.; Hansen, T.; Churchill, M. R. J. Am. Chem. Soc. 2000, 122, 3063-3070.
41. For general discussions on mechanisms of C-H hydroxylation, see: (a) Groves, J. T. J. Inorg. Biochem. 2006, 100, 434-447.
42. (b) Newcomb, M.; Toy, P. H. Acc. Chem. Res. 2000, 33, 449-455.
43. -1, see: Choi, S.-Y.; Toy, P. H.; Newcomb, M. J. Org. Chem. 1998, 63, 8609-8613.
44. Simakov, P. A.; Choi, S.-Y.; Newcomb, M. Tetrahedron Lett. 1998, 39, 8187-8190.
45. 2 of 0.87. See Supporting Information for additional details.
46. 1) was recorded in experiments with PhI=NNs as oxidant, see: (a) Müller, P.; Baud, C; Nägeli, I. J. Phys. Org. Chem. 1998, 11, 597-601.
47. (b) Nägeli, I.; Baud, C.; Bernardineili, G.; Jacquier, Y.; Moran, M.; Müller, P. Helv. Chim. Acta 1997, 80, 1087-1105.
48. +-constants.
49. Wang, J.; Chen, B.; Bao, J. J. Org. Chem. 1998, 63, 1853-1862.
50. Davies, H. M. L.; Jin, Q.; Ren, P.; Kovalevsky, A. Y. J. Org. Chem. 2002, 67, 4165-4169.
51. Preparation of and reactions with this catalyst will be described in a future manuscript, see: Kim, M.; Du Bois, J., manuscript in preparation.
52. For other examples of asymmetric C-H amination under Rh-catalysis, see: (a) Fruit, C.; Müller, P. Helv. Chim. Acta 2004, 87, 1607-1615.
53. (b) Liang, J.-L.; Yuan, S.-X.; Chan, P. W. H.; Che, C.-M. Tetrahedron Lett. 2003, 44, 5917-5920. Also, see ref 3c.
54. 3 yields 55% of the benzylic amine 10 and <10% of 11.
55. For ring-opening of a cyclopropylalkoxy radical, see: DePuy, C. H.; Dappen, G. M.; Hausser, J. W. J. Am. Chem. Soc. 1961, 83, 3156-3157.
56. In general, the solution color changes from green to red for all reactions as the dropwise addition of oxidant nears completion. When an excess of substrate is employed, the green color persists throughout the reaction course.
57. Wilson, C. R.; Taube, H. Inorg. Chem. 1975, 14, 2276-2279.
58. Gas chromatography and HPLC analysis of spent reaction mixtures have never revealed products of benzene amination/aziridination.
59. 3+ complexes has been described, see ref 37 and: Kadish, K. M.; Das, K.; Howard, R.; Dennis, A.; Bear, J. L. Bioelectrochem. Bioenerg. 1978, 5, 741-753.
60. 2 is readily prepared on scale (40 g) and is available from Aldrich Chemical Co.
61. 2 catalyst, thereby facilitating product purification.