Cobalt-carbene complex with single-bond character: Intermediate for the cobalt complex-catalyzed cyclopropanation

Journal of the American Chemical Society

Volumn 124, Issue 51, 2002, Pages 15152-15153

  Ikeno, Taketo ^a   Iwakura, Izumi ^a   Yamada, Tohru ^a  

^a KEIO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENE; COBALT COMPLEX;

ARTICLE; CATALYSIS; CHEMICAL BOND; CYCLOPROPANATION; ELECTRON; ENANTIOSELECTIVITY; INFRARED SPECTROSCOPY; REACTION ANALYSIS; VIBRATION;

EID: 0037176284     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja027713x     Document Type: Article

References (29)

1. Nozaki, H.; Moriuti, S.; Takaya, H.; Noyori, R. Tetrahedron Lett. 1966. 5239.
2. (a) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds; John Wiley & Sons: New York, 1998.
3. (b) Doyle, M. P.; Forbes. D. C. Chem. Rev. 1998, 98, 911.
4. (a) Lowenthal, R. E.; Abiko, A.; Masamune, S. Tetrahedron Lett. 1990. 31, 6005.
5. (b) Evans, D. A.; Woerpel, K. A.; Hinman, M. M.; Faul, M. M. J. Am. Chem. Soc. 1991, 113, 726.
6. Nishiyama, H.; Itoh, Y.; Matsumoto, H.; Park, S.-B.; Itoh, K. J. Am. Chem. Soc. 1994, 116, 2223.
7. (a) Ikeno, T.; Sato, M.; Sekino, H.; Nishizuka, A.; Yamada, T. Bull. Chem. Soc. Jpn. 2001, 74, 2139.
8. (b) Ikeno, T.; Iwakura, I.; Yabusbita, S.; Yamada, T. Org. Lett. 2002, 4, 517.
9. Fukuda, T.; Katsuki, T. Synlett 1995, 825.
10. For recent articles of the theoretical analysis of the cyclopropanation, see: (a) Fraile, J. M.; García, J. I.; Martínez-Merino, V.; Mayoral, J. A.; Salvatella, L. J. Am. Chem. Soc. 2001, 123, 7616.
11. (b) Bühl, M.; Terstegen, F.; Löffler, F.: Meynhardt, B.; Kierse, S.; Müller, M: Näther, C.; Lüning, U. Eur. J. Org. Chem. 2001, 2151.
12. (c) Rasmussen, T.; Jensen, J. F.; Ostergaard, N.; Tanner, D.; Ziegler, T.; Norrby, P.-O. Chem. Eur. J. 2002, 8, 177.
13. Previous reports on the observation of metal-carbene intermediates in metal-caltalyzed cyclopropanation, see: (a) Straub, B. F.; Hofmann, P. Angew. Chem., Int. Ed. 2001, 40, 1288.
14. (b) Park, S.-B.; Sakata, N.; Nisbiyama, H. Chem. Eur. J. 1996, 2, 303.
15. IR spectra were measured in the ATR configuration using a liquid cell under N2. A background scan was first done with a solution of 0.1 mmol complex in 2 mL of dichloromethane. After 0.1 mmol methyl diazoacetate was added to the circle cell as time zero, the sample measurements of the reaction media were performed.
16. -1 immediately after the addition of the methyl diazoacetate. On the contrary, when the Co complexes 3-6 were used, the dimers were hardly detected.
17. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, I. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.: Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.6; Gaussian, Inc.: Pittsburgh, PA, 1998.
18. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
19. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
20. Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
21. The measurement of magnetic susceptibility of Co complex revealed that the spin multiplicity of the starting Co(II) and Co(III) complex was doublet and triplet, respectively.
22. Valid structures of the Co(III) complexes 10 and 12 could not be obtained in the singlet states.
23. Relative energies are shown in the Supporting Information.
24. The influence of the basis set is described in the Supporting Information.
25. Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. J. Chem. Phys. 1985, 83, 735.
26. Reed, A. E.: Curtiss, L. A.: Weinhold, F. Chem. Rev. 1988, 88, 899.
27. (a) Baratta, W.; Herdtweck, E.; Herrmann, W.; Rigo, P.; Schwarz, J. Organometallics 2002, 21, 2101.
28. (b) Plaia, U.; Stolzenberg, H.; Fehlhammer, W. P. J. Am. Chem. Soc. 1985, 107, 2171.
29. Since p-orbital of carbene carbon conjugated with C=O bond, s-cis conformation was the most stable.