A computational study on addition of grignard reagents to carbonyl compounds

Journal of Organic Chemistry

Volumn 67, Issue 26, 2002, Pages 9346-9353

  Yamazaki, Shoko ^a   Yamabe, Shinichi ^a  

^a NARA UNIVERSITY OF EDUCATION   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AGGREGATION NATURE; REACTION PATH;

AGENTS; BOND STRENGTH (CHEMICAL); MAGNESIUM COMPOUNDS; PROBABILITY DENSITY FUNCTION;

CARBONYLATION;

CARBONYL DERIVATIVE; DIMER; DIMETHYL ETHER; FORMALDEHYDE; MAGNESIUM DERIVATIVE; METHYLMAGNESIUM CHLORIDE; REAGENT; UNCLASSIFIED DRUG;

ADDITION REACTION; ARTICLE; ATOM; CHEMICAL BOND; ELECTRON TRANSPORT; GEOMETRY; GRIGNARD REACTION; STEREOCHEMISTRY; THEORY;

EID: 0037184844     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo026017c     Document Type: Article

References (42)

1. (a) Grignard, V. C. R. Hebd. Seances Acad. Sci. 1900, 130, 1322.
2. (b) Handbook of Grignard Reagents; Silvermann, G. S., Rakita, P. E., Eds.; Marcel Dekker: New York, 1996.
3. (c) Grignard Reagents New Developments, Richey, H. G., Jr., Ed.; Wiley: New York, 2000.
4. (d) Wakefield, B. J. In Organomagnesium Methods in Organic Synthesis; Academic Press: London, 1995.
5. (e) Kharasch, M. S.; Reinmuth, O. In Grignard Reactions of Nonmetallic Substances; Prentice-Hall: Englewood Cliffs, NJ, 1954.
6. (f) Ashby, E. C. Pure Appl. Chem. 1980, 52, 545.
7. (g) Ashby, E. C.; Becker, W. E. J. Am. Chem. Soc. 1963, 85, 118.
8. (h) Maruyama, K.; Katagiri, T. J. Am. Chem. Soc. 1986, 108, 6263.
9. (i) Holm, T. Acta Chem. Scand. 1966, 20, 2821.
10. (j) Smith, S. G.; Su, G. J. Am. Chem. Soc. 1964, 86, 2750.
11. (k) Ashby, E. C.; Laemmle, J.; Newmann, H. M. Acc. Chem. Res. 1974, 7, 272.
12. (l) Yamataka, H.; Matsuyama, T.; Hanafusa, T. J. Am. Chem. Soc. 1989, 111, 4912.
13. (a) Still, W. C.; McDonald, J. H., III. Tetrahedron Lett. 1980, 21, 1031.
14. (b) Ko, K.-Y.; Eliel, E. L. J. Org. Chem. 1986, 51, 5353.
15. (c) Frye, S. V.; Eliel, E. L. J. Am. Chem. Soc. 1988, 110, 484.
16. Cram, D. J.; Kopecky, K. R. J. Am. Chem. Soc. 1959, 81, 2748.
17. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
18. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1998, 37, 785.
19. Onsager, L. J. Am. Chem. Soc. 1938, 58, 1486.
20. 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.; Baboul, A. G.; 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.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A. 7; Gaussian, Inc., Pittsburgh, PA, 1998.
21. Schlenk, W.; Schlenk, W., Jr. Ber. Dtsch. Chem. Ges. 1929, 62, 920.
22. Axten, J.; Troy, J.; Jiang, P.; Trachtman, M.; Bock, C. W. Struct. Chem. 1994, 99, 5.
23. (a) Spek, A. L.; Voorbergen, P.; Schat, G.; Blomberg, C.; Bickelhaupt, F.; J. Organomet. Chem. 1974, 77, 147.
24. (b) Toney, J.; Stucky, G. D. J. Chem. Soc., Chem. Commun, 1967, 1168.
25. (a) Swain, C. G.; Boyles, H. B. J. Am. Chem. Soc. 1951, 73, 870.
26. (b) Ashby, E. C.; Duke, R. B.; Newmann, H. M. J. Am. Chem. Soc. 1964, 89, 1967.
27. Carey, F. A.; Sundberg, R. J. In Advanced Organic Chemistry Part B: Reactions and Synthesis; Plenum Press: New York, 1990; p 376.
28. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016.
29. 2Mg bridged isomers were confirmed to be less stable than 6 or 13, respectively.
30. Marsch, M.; Harms, K.; Massa, W.; Boche, G.; Angew. Chem., Int. Ed. Engl. 1987, 26, 696.
31. Miles, W. H.; Rivera, S. L.; del Rosario, J. D. Tetrahedron Lett. 1992, 33, 305.
32. (a) Seebach, D.; Syfrig, M. A. Angew. Chem., Int. Ed. Engl. 1984, 23, 248.
33. (b) Seebach, D.; Hansen, J.; Seiler, P.; Gromek, J. M. J. Organomet. Chem. 1985, 285, 1.
34. (c) Zhang, P.; Gawley, R. E. Tetrahedron Lett. 1992, 33, 2945.
35. McGarvey, G. J.; Kimura, M. J. Org. Chem. 1982, 47, 5422.
36. When the Mg - O distance is decreased, the Mg - C distance is enlarged gradually. The partial optimizations with a fixed Mg - O distance were repeated, and a complex potential surface with various extremely shallow energy minima was found. A local minimum with smaller relative energy than that (=8.5 kcal/mol) of 23 (TS) was sought. However, the attempted geometry converged to that of 24 probably due to the complex potential curve and spin contamination, and 24 was calculated to be slightly less stable than 23 (TS).
37. The second Mg - O approach is possible via a route corresponding to 8 → 10 → 12 in Figure S2. A symmetric singlet-spin radical geometry 25 was obtained. Since four radical centers are distant with each other, triplet and quartet spin states have almost the same energies as that of the open singlet (25). The triplet or quartet radicals have also the same symmetric structures as that of 25. The triplet or quartet radicals would be related to intermediates detected by ESR spectroscopy (ref 1h and (a) Maruyama, K.; Hayashi, J.; Takagiri, T. Chem. Lett. 1987, 731. (b) Maruyama, K. Bull. Chem. Soc. Jpn. 1964, 37, 897).
38. The second Mg - O approach is possible via a route corresponding to 8 → 10 → 12 in Figure S2. A symmetric singlet-spin radical geometry 25 was obtained. Since four radical centers are distant with each other, triplet and quartet spin states have almost the same energies as that of the open singlet (25). The triplet or quartet radicals have also the same symmetric structures as that of 25. The triplet or quartet radicals would be related to intermediates detected by ESR spectroscopy (ref 1h and (a) Maruyama, K.; Hayashi, J.; Takagiri, T. Chem. Lett. 1987, 731. (b) Maruyama, K. Bull. Chem. Soc. Jpn. 1964, 37, 897).
39. (a) Holm, T. Acta Chem. Scand. 1991, 45, 925.
40. (b) Coburn, E. R. Organic Synthesis; Wiley & Sons: New York, 1955; Collect. Vol. No. III, p 696.
41. (c) Munch-Petersen, J. Organic Synthesis; Wiley & Sons: New York, 1973; Collect. Vol. No. V, p 762.
42. (d) Prout, F. S.; Hartman, R. J.; Huang, P.-Y.; Korpics, C. J.; Tichelaar, G. R. Organic Synthesis; Wiley & Sons: New York, 1963; Collect. Vol. No. IV, p 93.