Synergetic dimetallic effects in Gaudemar/Normant coupling between allylzinc and vinyl grignard reagents [11]

Journal of the American Chemical Society

Volumn 121, Issue 37, 1999, Pages 8665-8666

  Hirai, Atsushi ^a   Nakamura, Masaharu ^a   Nakamura, Eiichi ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; REAGENT; VINYL DERIVATIVE; ZINC DERIVATIVE;

CHEMICAL REACTION; CHEMICAL REACTION KINETICS; LETTER; REACTION ANALYSIS; STEREOCHEMISTRY; THERMODYNAMICS;

EID: 0033595561     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9914590     Document Type: Letter

References (28)

1. In consonance with the intuition, model B3LYP/6-31+G* calculations indicated that 1,1-dianion formation is 108 kcal/mol endothermic and the adduct would tend to decompose back to the two anions.
2. Gaudemar, M. C. R. Acad. Sci. Paris, Ser. C 1971, 273, 1669-1672.
3. (a) Knochel, P.; Normant, J.-F. Tetrahedron Lett. 1986, 27, 1039-1043.
4. (b) Review: Normant, J.-F.; Marek, I.; Lefrançois, J.-M. Pure Appl. Chem. 1992, 64, 1857-1864. Suzuki, K.; Imai, T.; Yamanoi, S.; Chino, M.; Matsumoto, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 2469-2471.
5. (b) Review: Normant, J.-F.; Marek, I.; Lefrançois, J.-M. Pure Appl. Chem. 1992, 64, 1857-1864. Suzuki, K.; Imai, T.; Yamanoi, S.; Chino, M.; Matsumoto, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 2469-2471.
6. Marek, I.; Normant, J.-F. Chem. Rev. 1996, 96, 3241-3267.
7. Nakamura, E.; Kubota, K.; Sakata, G. J. Am. Chem. Soc. 1997, 119, 5457-5458.
8. The GAUSSIAN 94 program was used. Ahlrichs's SVP (Schäfer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97, 2571-2577) all-electron basis set was used for the zinc atom and the 6-31+G* basis set for other atoms (denoted here as B3LYP/631A). For the computational method, see: Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844- 5845. As was the case with this report, HF/321A geometries (but not energetics) were in good accord with the B3LYP/631A geometries, and may be uesd as a much cheaper substitute of the latter.
9. The GAUSSIAN 94 program was used. Ahlrichs's SVP (Schäfer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97, 2571-2577) all-electron basis set was used for the zinc atom and the 6-31+G* basis set for other atoms (denoted here as B3LYP/631A). For the computational method, see: Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845. As was the case with this report, HF/321A geometries (but not energetics) were in good accord with the B3LYP/631A geometries, and may be uesd as a much cheaper substitute of the latter.
10. Prototypes of the heterodimer CP1 (e.g., homo μ-chloro-bridged dimers of halomagnesiurn and halozinc species) are well-known. See: Al-Juaid, S. S.; Eaborn, C.; Habtemariam, A.; Hitchcock, P. B.; Smith, J. D.; Tavakkoli, K.; Webb, A. D. J. Organomet. Chem. 1993, 462, 45-55.
11. 2. The details will be discussed in a full paper.
12. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Chem. Soc., Faraday Trans. 1994, 29, 1789-1798. Kubota, K.; Mori, S.; Nakamura, M.; Nakamura, E. J. Am. Chem. Soc. 1998, 120, 13334-13341.
13. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Chem. Soc., Faraday Trans. 1994, 29, 1789-1798. Kubota, K.; Mori, S.; Nakamura, M.; Nakamura, E. J. Am. Chem. Soc. 1998, 120, 13334-13341.
14. 2 atom as well as on the C-C double bond of the allyl group. This picture suggests that the reaction has the character of nucleophilic allylation of olefin.
15. Laloë, E.; Srebnik, M. Tetrahedron Lett. 1994, 35, 5587-5591.
16. Marek, I.; Lefrançois, J.-M.; Normant, J.-F. J. Org. Chem. 1994, 59, 4154-4161.
17. Andrews, P. C.; Raston, C. L.; Skelton, B. W.; White, A. H. Organometallics 1998, 17, 779-782.
18. Marek, I.; Lefrançois, J.-M.; Normant, J.-F. Synlett 1992, 633-634.
19. cis- and trans-crotylzinc reagents in solution are in rapid equilibrium with each other and hence we need only to compare the energies of isomeric TSs.
20. For theoretical studies on polymetallic effects and references, see: Nakamura M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080. Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-489. Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900-4910. Mori, S.; Nakamura, E. Chem. Eur. J. 1999, 5, 1534-1543. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845.
21. For theoretical studies on polymetallic effects and references, see: Nakamura M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080. Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-489. Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900-4910. Mori, S.; Nakamura, E. Chem. Eur. J. 1999, 5, 1534-1543. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845.
22. For theoretical studies on polymetallic effects and references, see: Nakamura M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080. Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-489. Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900-4910. Mori, S.; Nakamura, E. Chem. Eur. J. 1999, 5, 1534-1543. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845.
23. For theoretical studies on polymetallic effects and references, see: Nakamura M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080. Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-489. Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900-4910. Mori, S.; Nakamura, E. Chem. Eur. J. 1999, 5, 1534-1543. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845.
24. For theoretical studies on polymetallic effects and references, see: Nakamura M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080. Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-489. Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900-4910. Mori, S.; Nakamura, E. Chem. Eur. J. 1999, 5, 1534-1543. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845.
25. For theoretical studies on polymetallic effects and references, see: Nakamura M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 11016-11017. Mori, S.; Kim, B. H.; Nakamura, M.; Nakamura, E. Chem. Lett. 1997, 1079-1080. Nakamura, E.; Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887-489. Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900-4910. Mori, S.; Nakamura, E. Chem. Eur. J. 1999, 5, 1534-1543. Nakamura, E.; Hirai, A.; Nakamura, M. J. Am. Chem. Soc. 1998, 120, 5844-5845.
26. Nakamura, E.; Miyachi, Y.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1992, 114, 6686-6692.
27. Marek, I.; Normant, J.-F. In Metal catalyzed cross coupling reactions; Diederich, F., Stang, P., Eds.; Wiley VCH: New York, 1998; pp 271-337.
28. 3D pictures and Cartesian coordinates are located at http://ww-w.chem.s.u-tokyo.ac.jp/∼common/Theo/GN1/title.html.