Osmium-Promoted Electrophilic Substitution of Anisoles: A Versatile New Method for the Incorporation of Carbon Substituents

Journal of Organic Chemistry

Volumn 62, Issue 1, 1997, Pages 130-136

  Kolis, Stanley P ^a   Kopach, Michael E ^a   Liu, Ronggang ^a   Harman, W Dean ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000649646     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961983e     Document Type: Article

References (23)

1. Roberts, R. M.; Khalaf, A. A. Friedel-Crafts Alkylation Chemistry: A Century of Discovery; M. Dekker: New York, 1984.
2. (a) Kopach, M. E.; Gonzalez, J.; Harman, W. D. J. Am. Chem Soc. 1991, 113, 8972.
3. (b) Kopach, M. E.; Harman, W. D. J. Org. Chem. 1994, 59, 6506.
4. Harman, W. D.; Sekine, M.; Taube, H. J. Am. Chem. Soc. 1988, 110, 5725.
5. For an example of a well characterized 4H-anisolium complex see reference 2b.
6. 3CN, 100 mV/s, TBAH. See reference 3.
7. Harman, W. D.; Taube, H. J. Am. Chem. Soc. 1987, 109, 1883.
8. For a review of rearrangements of alkylating agents and alkyl substituents, see reference 1, Chapters 2 and 8 and references therein.
9. Nagaoka, T.; Berinstain, D; Griller, A. B.; Wayner, D. D. M. J. Org. Chem. 1990, 55, 3707.
10. a of about -8 in water for the osmiumf(II) complex.
11. Winemiller, M. D.; Kopach, M. E.; Harman, W. D. Submitted for publication.
12. (a) Kopach, M. E.; Hipple, W. G.; Harman, W. D. J. Am. Chem. Soc. 1992, 114, 1737.
13. (b) Kopach, M. E.; Harman, W. D. J. Am. Chem. Soc. 1994, 116, 6581.
14. Kolis, S. P.; Gonzalez, J.; Bright, L. M.; Harman, W. D. Orgonometallics 1996, 15, 245.
15. 2-4H-anisolium)]2+ has been determined to be -3.6 ± 1 whereas that for acetonitrililium cation is -10. See reference 10.
16. We have observed electrophilic addition reactions to aromatic rings of pentaainmineosmium(II) complexes for phenols, anilines, pyrroles, furans, and napththalenes, and in all cases encountered, the electrophile adds to the exo face of the ring.
17. 3).
18. Kopach, M. E.; Kolis, S. P.; Liu, R.; Harman, W. D. Manuscript in preparation.
19. For a good review of ayrlcuprates used in conjugate addition reactions see Lipshutz, B. H.; Sengupta, S. Organic Reactions; Paquette, L. A., Ed.; John Wiley and Sons: New York, 1992; Vol. 41.
20. See for example Cho, C. S.; Motofusa, S.; Ohe, K.; Uemura, S. J. Org. Chem. 1995, 60, 883.
21. Call, J. T.; Hughes, K. A.; Harman, W. D.; Finn, M. G. Inorg. Chem. 1993, 32, 2123.
22. 3 in 98% overall yield (see reference lc). Using these procedures, the cost of any of the final organic products presented in Table 5 falls in the range of $30-35/g. This reflects the cost of osmium over the entire six-step process (taking into account yields) and assumes no recovery of the metal.
23. Please see supporting information for full characterization data for all compounds. For full description of general experimental details, please see ref 11b.