Catalytic intermolecular linear allylic C-H amination via heterobimetallic catalysis

Journal of the American Chemical Society

Volumn 130, Issue 11, 2008, Pages 3316-3318

  Reed, Sean A ^a   White, M Christina ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZOQUINONE; CARBON; CHROMIUM; HYDROGEN; NITROGEN; PALLADIUM;

ANALYTIC METHOD; ARTICLE; BIOLOGICAL ACTIVITY; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY;

ALKENES; AMINATION; AMINES; CATALYSIS; CHROMIUM; LIGANDS; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; PALLADIUM; STEREOISOMERISM;

EID: 41449083866     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja710206u     Document Type: Article

References (47)

1. Kibayashi, C. Chem. Pharm. Bull. 2005, 53, 1375.
2. (a) Mitsunobu, O. Synthesis 1981, 1.
3. (b) Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395.
4. (c) Johannsen, M.; Jorgensen, K. A. Chem. Rev. 1998, 98, 1689 and references therein.
5. (d) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743.
6. (e) Ohmura, T.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 15164.
7. Streamlining syntheses via late-stage C-H oxidation, see: (a) Fraunhoffer, K. J.; Bachovchin, D. A.; White, M. C. Org. Lett. 2005, 7, 223.
8. (b) Covell, D. J.; Vermeulen, N. A.; Labenz, N. A.; White, M. C. Angew. Chem., Int. Ed. 2006, 45, 8217.
9. (c) Hoffman, R. W. Synthesis 2006, 21, 3531.
10. For examples of late staize C-H hydroxylation and animation, see: (d) Chen, M. S.; White, M. C. Science 2007, 318, 783.
11. (e) Wender, P. A.; Hilinski, M. K.; Mavweg, A. V. W. Org. Lett. 2005, 7, 79.
12. (f) Hinman, A.; Du Bois, J. J. Am. Chem. Soc. 2003, 125, 11510.
13. (a) Fraunhoffer, K. J.; White, M. C. J. Am. Chem. Soc. 2007, 129, 7274.
14. 4NOAc to the intramolecular C-H animation significantly reduced yields, see ref 4a.
15. Intramolecular C-H animation via nitrenes: (a) Espino, C. C.; Fiori, K. W.; Kim, M.; Du Bois, J. J. Am. Chem. Soc. 2004, 126, 15378 and references therein,
16. (b) Lebel, H.; Huard, K.; Lectard, S. J. Am. Chem. Soc. 2005, 127, 14198.
17. Intermolecular C-H animations via nitrenes: (a) Fiori, K. W.; Du Bois, J. J. Am. Chem. Soc. 2007, 129, 562.
18. (b) Liang, C.; Robcrt-Peillard, F.; Fruit, C.; Muller, P.; Dodd, R. H.; Daubin, P. Angew. Chem., Int. Ed. 2006, 45, 4641.
19. (c) Yang, J.; Weinberg, R.; Breslow, R. Chem. Commun. 2000, 531.
20. (d) Yu, X.-Q.; Huans, J.-S.; Zhou, X.-G.; Che, C.-M. Org. Lett. 2000, 2, 2233.
21. (e) Liang, C.; Collet, F.; Peillard, F. R.; Muller, P.; Dodd, R. H.; Dauben, P. J. Am. Chem. Soc 2007, 130, 343.
22. Intermolecular allylic C-H animations using excess olefin: (a) Kalita, B.; Nicholas, K. M. Tetrahedron Lett. 2005, 46, 1451.
23. (b) Aburel, P. S.; Zhuang, W.; Hazell, R. C.; Jorgensen, K. A. Org. Biomol. Chem. 2005, 3, 2344.
24. Rogers, M. M.; Kotov, V.; Chatwichien, J.; Stahl, S. S. Org. Lett. 2007, 9, 4331, and references therein.
25. Trost, B. M.; Keinan, E. J. Org. Chem. 1979, 44, 3451.
26. For examples of cooperative heterobimetallic catalysis see: (a) Kamijo, S.; Yamamoto, Y. In Multimetallic Catalysts in Organic Synthesis; Shibasaki, M., Yamamoto, Y., Eds.; Wiley-VCH: New York, 2004; Chapter I.
27. For examples from asymmetric catalysis see: (b) Sawamura, M.; Sudoh, M.; Ito, Y. J. Am. Chem. Soc. 1996, 118, 3309.
28. (c) Sammis, G. M.; Danjo, H.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 9928.
29. Covell, D. J.; White, M. C. Manuscript in preparation.
30. Commercial (1S,2S)-(+)-[1,2-cyclohexanediamino-N,N′- bis(3,5-di-tert-butylsalicylidene)]Cr(III)Cl was used.
31. Increasing 2 loadings gave an increased rate of conversion but a decrease in product yields (SI). Gas Chromatograph (GC) peaks consistent with olefin isomerization were observed with higher loadings of 2.
32. Branched reaioselectivity with 1: (a) Chen, M. S.; Prabagaran, N.; Labenz, N. A.; White, M. C. J. Am. Chem. Soc. 2005, 127, 6970.
33. (b) Fraunhoffer, K. J.; Prabagaran, N.; Sirois, L. E.; White, M. C. J. Am. Chem. Soc. 2006, 128, 9032.
34. (c) Delcamp, J. H.; White, M. C. J. Am. Chem. Soc. 2006, 128, 15076.
35. (d) Reference 4a.
36. Conn, C.; Shimmon, R.; Cordaro, F.; Hargraves, T. L.; Ibrahim, P. Bioorg. Med. Chem. Lett. 2001, 11, 2565.
37. (a) Racherla, U. S.; Brown, H. C. J. Org. Chem. 1991, 56, 401.
38. (b) Kubota, K.; Leighton. J. L. Angew. Chem., Int. Ed. 2003, 42, 946.
39. (c) Cogan, D. A.; Liu, G.; Ellman, J. Tetrahedron 1999, 55, 8883.
40. (d) Evans, D. A.; Ennis, M. D.; Mature, D. J. J. Am. Chem. Soc. 1982, 104, 1737.
41. (e) Myers, A. G.; Yang, B. H.; Chen, H.; McKinstry, L.; Kopeckv, D. J.; Gleason, J. L. J. Am. Chem. Soc. 1997, 119, 6496.
42. Reginato, G.; Gaggini, F.; Mordini, A.; Valacchi, M. Tetrahedron 2005, 61, 6791.
43. Norrild, J. C.; Pedersen, C.; Sotofte, I. Carbohydr. Res. 1997, 297, 261.
44. Raju, B.; Anandan, S.; Gu, S.; Herradura, P.; O'Dowd, H.; Kim, B.; Gomez, M.; Hackbarth, C.; Wu, C.; Wang, W.; Yuan, Z.; White, R.; Trias, J.; Patel, D. V. Bioorg. Med. Chem. Lett. 2004, 14, 3103.
45. Allylic acetates were the other major product observed (see SI). This is consistent with the catalytic reaction where allylic acetates are the major byproduct. When allylic acetates are exposed to the reaction conditions, only trace (∼6%) allylic carbamate is formed with different regio- and stereoselectivities than those observed under catalytic conditions (SI).
46. Cr(salen) may bind to and enhance the π-acidity of the BQ, thereby activating the π-allylPd species towards functionalization. Cr(salen) has been demonstrated to activate BQ towards Diels-Alder reactions: Jarvo, E. R.; Lawrence, B. M.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2005, 44, 6043.
47. Cr(salen) may deliver the carbamate nucleophile while BQ activates the π-allylPd towards functionalization. Cr(salen) has been shown to activate azide nucleophiles: Hansen, K. B.; Leighton, J. L.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 10924. For BQ acting as a π-acidic ligand to promote functionalization of π-allylPd with acetate in an allylic C-H oxidation reaction, see ref 14a.