Observation and iodine oxidation of the protonated anionic propargyltungsten species formed in the reaction of fischer-type carbene complexes with alkynyllithiums

Organometallics

Volumn 16, Issue 24, 1997, Pages 5137-5139

  Iwasawa, Nobuharu ^a   Ochiai, Takashi ^a   Maeyama, Katsuya ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000334730     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om970835r     Document Type: Article

References (13)

1. (a) Iwasawa, N.; Maeyama, K.; Saitou, M.; J. Am. Chem. Soc. 1997, 119, 1486.
2. (b) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918.
3. (a) Frühauf, H.-W. Chem. Rev. 1997, 97, 523.
4. (b) Welker, M. E. Chem. Rev. 1992, 92, 97 and references cited therein.
5. A similar type of anionic 1,2-migration of pentacarbonyltungsten was also observed in the following examples: (a) Fischer, H.; Meisner, T.; Hofmann, J. Chem. Ber. 1990, 723, 1799. (b) Dötz, K. H.; Christoffers, C.; Knochel, P. J. Organomet. Chem. 1995, 489, C84. (c) Barluenga, J.; Tomas, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (d) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88.
6. A similar type of anionic 1,2-migration of pentacarbonyltungsten was also observed in the following examples: (a) Fischer, H.; Meisner, T.; Hofmann, J. Chem. Ber. 1990, 723, 1799. (b) Dötz, K. H.; Christoffers, C.; Knochel, P. J. Organomet. Chem. 1995, 489, C84. (c) Barluenga, J.; Tomas, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (d) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88.
7. A similar type of anionic 1,2-migration of pentacarbonyltungsten was also observed in the following examples: (a) Fischer, H.; Meisner, T.; Hofmann, J. Chem. Ber. 1990, 723, 1799. (b) Dötz, K. H.; Christoffers, C.; Knochel, P. J. Organomet. Chem. 1995, 489, C84. (c) Barluenga, J.; Tomas, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (d) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88.
8. A similar type of anionic 1,2-migration of pentacarbonyltungsten was also observed in the following examples: (a) Fischer, H.; Meisner, T.; Hofmann, J. Chem. Ber. 1990, 723, 1799. (b) Dötz, K. H.; Christoffers, C.; Knochel, P. J. Organomet. Chem. 1995, 489, C84. (c) Barluenga, J.; Tomas, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (d) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaría, J.; Carbajo, R. J.; López-Ortiz, F.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88.
9. 13C NMR Data for Organometallic Compounds; Academic Press: London, 1981.
10. Although it is certain there is direct σ bonding between tungsten and the labeled carbon, we have not yet ruled out several other possibilities such as A and B for the exact structure of this intermediate. equation presented
11. For related reactions, see the following references: (a) Shieh, S.-J.; Chen, C.-C.; Liu, R.-S. J. Org. Chem. 1997, 62, 1986. (b) Shu, H.-G.; Shiu, L.-H.; Wang, S.-H.; Wang, S.-L.; Lee, G.-H.; Peng, S.-M.; Liu, R.-S. J. Am. Chem. Soc. 1996, 118, 530. See also ref 2b.
12. For related reactions, see the following references: (a) Shieh, S.-J.; Chen, C.-C.; Liu, R.-S. J. Org. Chem. 1997, 62, 1986. (b) Shu, H.-G.; Shiu, L.-H.; Wang, S.-H.; Wang, S.-L.; Lee, G.-H.; Peng, S.-M.; Liu, R.-S. J. Am. Chem. Soc. 1996, 118, 530. See also ref 2b.
13. For the simplicity of the reaction procedure, addition of a large excess of MeOH at -78 °C was employed instead of adding 10 mol equiv of MeOH and raising the temperature to -50 °C. Protonation occurs completely under these conditions.