Proposal for the metallacycle pathway during the cyclopropanation catalyzed by cobalt-schiff base complexes

Organic Letters

Volumn 6, Issue 6, 2004, Pages 949-952

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

^a KEIO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; COBALT COMPLEX; ETHYLENE DERIVATIVE; SCHIFF BASE;

ARTICLE; CATALYSIS; COMPLEX FORMATION; CYCLOPROPANATION; DENSITY FUNCTIONAL THEORY; METALLATION;

EID: 1642487651     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol036505m     Document Type: Article

References (27)

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9. (c) Ikeno, T.; Iwakura, I.; Yabushita, S.; Yamada, T. Org. Lett. 2002, 4, 517-520.
10. (d) Ikeno, T.; Iwakura, I.; Yamada, T. J. Am. Chem. Soc. 2002, 124, 15152-15153.
11. (a) 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, J. 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, revisions A.6 and A.11; Gaussian, Inc.: Pittsburgh, PA, 1998.
12. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
13. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
14. These basis sets afforded the same results. Possible rotational isomers were fully optimized, and the energies were compared with each other. See Supporting Information.
15. S2 values are shown. 5a, S2 = 0.763; 5b, S2 = 3.759; 6a, S2 = 0.820; 6b, S2 = 3.832; 7a, S2 = 0.769; 7b, S2 = 3.786; 8a, S2 = 0.792; 8b, S2 = 3.751.
16. A number of the rotational isomers in the carbene moiety were omitted for clarity. S2 values are shown. 4a, S2 = 0.764; 4b, S2 = 0.765; 4d, S2 = 3.761; 9a, S2 = 0.826; 9b, S2 = 0.821; 9d, S2 = 3.784; 9e, S2 = 3.784; 9f, S2 = 3.787; 10a, S2 = 0.766; 10b, S2 = 0.765; 10c, S2 = 0.762; 10d, S2 = 3.783; 10e, S2 = 3.782; 10f, S2 = 3.787; 10g, S2 = 0.764; 10h, S2 = 0.776; 11a, S2 = 0.813; 11b, S2 = 0.814; 11c, S2 = 0.773; 11d, S2 = 3.801; 11e, S2 = 3.801; 11f, S2 = 3.805; 11g, S2 = 0.786; 12, S2 = 0.795; 13, S2 = 0.773.
17. 1) 9 and carbene complex 10 were both in the doublet states and were stable. It was experimentally observed that the green-colored [bis(salicylidene-N-phenethyl)]cobalt(II) complex turned red during the reaction with a diazo compound. The spin crossing could be considered during this process, though not mentioned. (a) Punniyamurthy, T.; Bhatia, B.; Iqbal, J. J. Org. Chem. 1994, 59, 850-853.
18. Energy differences between the doublet and quartet states in the bridged complexes were much greater than those in the unbridged complexes. These results would also support the fact that the ethylene bridge could retain the planarity of the complex to stabilize the low-spin state.
19. Ethylene complexes coordinated on the equatorial position parallel to the cobalt-carbene carbon bond 10g and perpendicular in 10h, and the axial positions of 10i and 10j were also optimized. The complexes 10i and 10j were found to be much less stable than complexes 10g and 10h.
20. 2 11g and 11b were ΔG = 21.0 and 23.8 kcal/mol, respectively. The mechanism via the cobaltacyclobutane was supported by these results and also on the basis of the Gibbs free energy.
21. In the presence of the 0.1 mmol cobalt(II) complex, the mixture of ethyl diazoacetate (0.3 mL) and cis (or trans) β-methylstyrene (0.3 mL) was heated at 90°C for 5 h. Only for the unbridged-complex-catalyzed reaction was the corresponding cyclopropane obtained and identified by TLC, GC, and NMR.
22. Proposals of mechanisms based on the experimental results: (a) Aratani, T.; Yoneyoshi, Y.; Nagase, T. Tetrahedron Lett. 1975, 1707-1710. (b) Aratani, T. Pure Appl. Chem. 1985, 57, 1839-1844. (c) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1986, 25, 1005-1006. (d) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Helv. Chim. Acta 1988, 71, 1553-1565. Proposals of mechanisms based on the theoretical analysis: (e) Fraile, J. M.; García, J.-I.; Martínez-Merino, V.; Mayoral, J. A.; Salvatella, L. J. Am. Chem. Soc. 2001, 123, 7616-7625. (f) Rasmussen, T.; Jensen, J. F.; Østergaard, N.; Tanner, D.; Ziegler, T.; Norrby, P.-O. Chem. - Eur. J. 2002, 8, 177-184.
23. Proposals of mechanisms based on the experimental results: (a) Aratani, T.; Yoneyoshi, Y.; Nagase, T. Tetrahedron Lett. 1975, 1707-1710. (b) Aratani, T. Pure Appl. Chem. 1985, 57, 1839-1844. (c) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1986, 25, 1005-1006. (d) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Helv. Chim. Acta 1988, 71, 1553-1565. Proposals of mechanisms based on the theoretical analysis: (e) Fraile, J. M.; García, J.-I.; Martínez-Merino, V.; Mayoral, J. A.; Salvatella, L. J. Am. Chem. Soc. 2001, 123, 7616-7625. (f) Rasmussen, T.; Jensen, J. F.; Østergaard, N.; Tanner, D.; Ziegler, T.; Norrby, P.-O. Chem. - Eur. J. 2002, 8, 177-184.
24. Proposals of mechanisms based on the experimental results: (a) Aratani, T.; Yoneyoshi, Y.; Nagase, T. Tetrahedron Lett. 1975, 1707-1710. (b) Aratani, T. Pure Appl. Chem. 1985, 57, 1839-1844. (c) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1986, 25, 1005-1006. (d) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Helv. Chim. Acta 1988, 71, 1553-1565. Proposals of mechanisms based on the theoretical analysis: (e) Fraile, J. M.; García, J.-I.; Martínez-Merino, V.; Mayoral, J. A.; Salvatella, L. J. Am. Chem. Soc. 2001, 123, 7616-7625. (f) Rasmussen, T.; Jensen, J. F.; Østergaard, N.; Tanner, D.; Ziegler, T.; Norrby, P.-O. Chem. - Eur. J. 2002, 8, 177-184.
25. Proposals of mechanisms based on the experimental results: (a) Aratani, T.; Yoneyoshi, Y.; Nagase, T. Tetrahedron Lett. 1975, 1707-1710. (b) Aratani, T. Pure Appl. Chem. 1985, 57, 1839-1844. (c) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1986, 25, 1005-1006. (d) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Helv. Chim. Acta 1988, 71, 1553-1565. Proposals of mechanisms based on the theoretical analysis: (e) Fraile, J. M.; García, J.-I.; Martínez-Merino, V.; Mayoral, J. A.; Salvatella, L. J. Am. Chem. Soc. 2001, 123, 7616-7625. (f) Rasmussen, T.; Jensen, J. F.; Østergaard, N.; Tanner, D.; Ziegler, T.; Norrby, P.-O. Chem. - Eur. J. 2002, 8, 177-184.
26. Proposals of mechanisms based on the experimental results: (a) Aratani, T.; Yoneyoshi, Y.; Nagase, T. Tetrahedron Lett. 1975, 1707-1710. (b) Aratani, T. Pure Appl. Chem. 1985, 57, 1839-1844. (c) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1986, 25, 1005-1006. (d) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Helv. Chim. Acta 1988, 71, 1553-1565. Proposals of mechanisms based on the theoretical analysis: (e) Fraile, J. M.; García, J.-I.; Martínez-Merino, V.; Mayoral, J. A.; Salvatella, L. J. Am. Chem. Soc. 2001, 123, 7616-7625. (f) Rasmussen, T.; Jensen, J. F.; Østergaard, N.; Tanner, D.; Ziegler, T.; Norrby, P.-O. Chem. - Eur. J. 2002, 8, 177-184.
27. Proposals of mechanisms based on the experimental results: (a) Aratani, T.; Yoneyoshi, Y.; Nagase, T. Tetrahedron Lett. 1975, 1707-1710. (b) Aratani, T. Pure Appl. Chem. 1985, 57, 1839-1844. (c) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1986, 25, 1005-1006. (d) Fritschi, H.; Leutenegger, U.; Pfaltz, A. Helv. Chim. Acta 1988, 71, 1553-1565. Proposals of mechanisms based on the theoretical analysis: (e) Fraile, J. M.; García, J.-I.; Martínez-Merino, V.; Mayoral, J. A.; Salvatella, L. J. Am. Chem. Soc. 2001, 123, 7616-7625. (f) Rasmussen, T.; Jensen, J. F.; Østergaard, N.; Tanner, D.; Ziegler, T.; Norrby, P.-O. Chem. - Eur. J. 2002, 8, 177-184.