An asymmetric nitro-Mannich reaction applicable to alkyl, aryl, and heterocyclic imines

Journal of Organic Chemistry

Volumn 70, Issue 14, 2005, Pages 5665-5670

  Anderson, James C ^a   Howell, Gareth P ^a   Lawrence, Ron M ^b   Wilson, Claire S ^a  

^a UNIVERSITY OF NOTTINGHAM   (United Kingdom)

^b GLAXOSMITHKLINE   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE; CATALYSIS; COPPER; SUBSTRATES;

CHIRAL LIGANDS; ENANTIOMERIC ACCESS (EA); NITRO-MANNICH REACTION; NITROAMINES; NONAROMATIC ALDIMINES;

REACTION KINETICS;

1,2 DIAMINE; 4 METHOXYBENZYLIMINE; ALDIMINE; ALKANE DERIVATIVE; AMINE; BETA NITROAMINE; COPPER DERIVATIVE; DIAMINE; HETEROCYCLIC COMPOUND; IMINE; LIGAND; NITROGEN DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; TRIMETHYLSILYLNITROPROPANATE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; CHIRALITY; ENANTIOMER; ENANTIOSELECTIVITY; MANNICH REACTION; NITRO MANNICH REACTION; PRODUCT PARAMETERS; PRODUCT YIELD;

EID: 22144481321     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo050762i     Document Type: Article

References (26)

1. Westermann, N. Angew. Chem., Int. Ed. (Highlight) 2003, 42, 151.
2. Lucet, D.; Le Gall, T.; Mioskowski, C. Angew. Chem., Int. Ed. 1998, 37, 2581.
3. Anderson, J. C.; Peace, S.; Pih, S. Synlett 2000, 850.
4. Knudsen, K. R.; Risgaard, T.; Nishiwaki, N.; Gothelf, K. V.; Jørgensen, K. A. J. Am. Chem. Soc. 2001, 123, 5843.
5. Nishiwaki, N.; Knudsen, K. R.; Gothelf, K. V.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2001, 40, 2992.
6. Yamada, K.; Harwood, S.; Groger, H.; Shibasaki, M. Angew. Chem., Int. Ed. 1999, 38, 3504.
7. Yamada, K. I.; Moll, G.; Shibasaki, M. Synlett 2001, 980.
8. Two recent contributions that do not involve organic catalysis are: (a) Lee, A.; Kim, W.; Lee, J.; Hyeon, T.; Kim, B. M. Tetrahedron: Asymmetry 2004, 15, 2595.
9. (b) Li, Z.; Li, C.-J. J. Am. Chem. Soc. 2005, 127, 3672.
10. Bernardi, L.; Bonini, B. F.; Capitò, E.; Dessole, G.; Comes-Franchini, M.; Fochi, M.; Ricci, A. J. Org. Chem. 2004, 69, 8168.
11. Okino, T.; Nakamura, S.; Furukawa, T.; Takemoto, Y. Org. Lett. 2004, 6, 625.
12. Yoon, T. P.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2005, 44, 466.
13. Nugent, B. M.; Yoder, R. A.; Johnston, J. N. J. Am. Chem. Soc. 2004, 126, 3418.
14. Anderson, J. C.; Blake, A. J.; Howell, G. P.; Wilson, C. S. J. Org. Chem. 2005, 70, 549-55.
15. tBu-BOX ligand 6c had a pronounced effect on the enantioselective addition of organolithiums to PMP imines. See: Denmark, S. E.; Stiff, C. M. J. Org. Chem. 2000, 65, 5875.
16. In retrospect we surveyed only aryl groups with electron withdrawing substituents. No donor groups, such as Me or MeO, were screened, but we anticipate they should also be satisfactory substrates.
17. Sisti, A. J.; Milstein, S. R. J. Org. Chem. 1974, 39, 3932-3936.
18. Barluenga, J.; Alejandro, M.; Fernández, F.; Aznar, F.; Valdés, C. Chem. Eur. J. 2004, 10, 494.
19. Iwamura, H. Bull. Chem. Soc. Jpn. 1974, 47, 193.
20. Highly colored samples of this imine afforded the product 3h in lower ee (70-80%). The origins of this effect are unknown.
21. The OMB protected imine of hexanal gives a diastereoselectivity of 90:10 without chiral ligand (ref 13).
22. Sturgess, M. A.; Yarberry, D. J. Tetrahedron Lett. 1993, 34, 4743-6.
23. 3h has 1R,2R stereochemistry, but the sense of stereoinduction is as drawn.
24. One could forward a plausible mechanism along the lines of that offered by Evans for enantioselective Henry reactions catalyzed by a copper acetate-bis(oxazoline) catalyst, but we feel this system is more complicated and awaits further investigation. See: Evans, D. A.; Seidel, D.; Rueping, M.; Lam, H. W.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2004, 125, 12692.
25. Aly, M. F.; Grigg, R. Tetrahedron 1988, 44, 7271.
26. All substrates screened needed 35-40 h to give good conversion.