Dearomatization of anilines by coordination to pentaammineosmium (II)

Organometallics

Volumn 15, Issue 1, 1996, Pages 245-259

  Kolis, Stanley P ^a   Gonzalez, Javier ^a   Bright, L Michael ^a   Harman, W Dean ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002575778     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om950747b     Document Type: Article

References (52)

1. Using catalytic hydrogenation (Rylander, P. N. In Catalytic Hydrogenation in Organic Synthesis; Academic Press: New York, 1979, p 1861, anilsness have been converted to bicyclic ring systems via intermediate aminocyclohexanes: (a) Snieckus, V. A.; Onouchi, T.; Boekelheide V. J. Org. Chem. 1972, 37, 2845. (b) Fraser, R. R.; Swingle, R. B. Can. J. Chem. 1970, 48, 2065. Using Birch reduction. have been selectively transformed into conjugated enamines used in carbon-carbon bond forming reactions: (c) Miaward, B. B. J. Chem. Soc. 1960, 26. (d) Birch, A. J.; Hutchinson, E. G.; Subba Rao, G. J. Chem. Soc., Chem. Commun. 1970, 657.
2. Using catalytic hydrogenation (Rylander, P. N. In Catalytic Hydrogenation in Organic Synthesis; Academic Press: New York, 1979, p 1861, anilsness have been converted to bicyclic ring systems via intermediate aminocyclohexanes: (a) Snieckus, V. A.; Onouchi, T.; Boekelheide V. J. Org. Chem. 1972, 37, 2845. (b) Fraser, R. R.; Swingle, R. B. Can. J. Chem. 1970, 48, 2065. Using Birch reduction. have been selectively transformed into conjugated enamines used in carbon-carbon bond forming reactions: (c) Miaward, B. B. J. Chem. Soc. 1960, 26. (d) Birch, A. J.; Hutchinson, E. G.; Subba Rao, G. J. Chem. Soc., Chem. Commun. 1970, 657.
3. Using catalytic hydrogenation (Rylander, P. N. In Catalytic Hydrogenation in Organic Synthesis; Academic Press: New York, 1979, p 1861, anilsness have been converted to bicyclic ring systems via intermediate aminocyclohexanes: (a) Snieckus, V. A.; Onouchi, T.; Boekelheide V. J. Org. Chem. 1972, 37, 2845. (b) Fraser, R. R.; Swingle, R. B. Can. J. Chem. 1970, 48, 2065. Using Birch reduction. have been selectively transformed into conjugated enamines used in carbon-carbon bond forming reactions: (c) Miaward, B. B. J. Chem. Soc. 1960, 26. (d) Birch, A. J.; Hutchinson, E. G.; Subba Rao, G. J. Chem. Soc., Chem. Commun. 1970, 657.
4. Using catalytic hydrogenation (Rylander, P. N. In Catalytic Hydrogenation in Organic Synthesis; Academic Press: New York, 1979, p 1861, anilsness have been converted to bicyclic ring systems via intermediate aminocyclohexanes: (a) Snieckus, V. A.; Onouchi, T.; Boekelheide V. J. Org. Chem. 1972, 37, 2845. (b) Fraser, R. R.; Swingle, R. B. Can. J. Chem. 1970, 48, 2065. Using Birch reduction. have been selectively transformed into conjugated enamines used in carbon-carbon bond forming reactions: (c) Miaward, B. B. J. Chem. Soc. 1960, 26. (d) Birch, A. J.; Hutchinson, E. G.; Subba Rao, G. J. Chem. Soc., Chem. Commun. 1970, 657.
5. Using catalytic hydrogenation (Rylander, P. N. In Catalytic Hydrogenation in Organic Synthesis; Academic Press: New York, 1979, p 1861, anilsness have been converted to bicyclic ring systems via intermediate aminocyclohexanes: (a) Snieckus, V. A.; Onouchi, T.; Boekelheide V. J. Org. Chem. 1972, 37, 2845. (b) Fraser, R. R.; Swingle, R. B. Can. J. Chem. 1970, 48, 2065. Using Birch reduction. have been selectively transformed into conjugated enamines used in carbon-carbon bond forming reactions: (c) Miaward, B. B. J. Chem. Soc. 1960, 26. (d) Birch, A. J.; Hutchinson, E. G.; Subba Rao, G. J. Chem. Soc., Chem. Commun. 1970, 657.
6. Portion of this work have been previously communicated: (a) Kopach M. E.; Gonzalez, J.; Harman, W. D. J. Am. Chem. Soc. 1991, 8972. (b) Gonzalez, J.; Sabet, M.; Harman, W. D. J. Am. Chem. Soc. 1983, 115, 8857.
7. Portion of this work have been previously communicated: (a) Kopach M. E.; Gonzalez, J.; Harman, W. D. J. Am. Chem. Soc. 1991, 8972. (b) Gonzalez, J.; Sabet, M.; Harman, W. D. J. Am. Chem. Soc. 1983, 115, 8857.
8. Harman, W. D.; Schaefer, W. P.; Taube, H. J. Am. Chem. Soc. 1990, 112, 2682.
9. Harman, W. D.; Taube, H. J. Am. Chem. Soc. 1988, 110, 5408.
10. 2) are abbreviated as Os(II) for clatity.
11. 3
12. Aufauvre, F.; Dantonnet, M.; Dondon, M. L. Bull. Soc. Chim. Fr. 1965, 12, 3566.
13. Harman, W. D.; Sekine, M.; Taube, H. J. Am. Chem. Soc. 1988, 110, 2439.
14. Andrews, L. J.; Keefer, R. M. J. Am. Chem. Soc. 1953, 75, 3776.
15. Cava, M. P.; Deana, A. A.; Muth, K.; Mitchell, M. J. Org. Syn. Coll. Vol. V 1973, 944.
16. -, presumably generated from trace amounts of water in the reagents.
17. 2a,33
18. Both δ-nucleophitic attack and α-protonation of the enolate are expected on the basis of litersture precedents: Cain, D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pargamon Press. Oxford, U.K., 1991; Vol, 9, p 50.
19. Semmelhack, M. F. Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, U.K., 1991; Vol. 2, p 517.
20. Mahaffy, C. A. L. Synth. React. Inorg. Met.-Org. Chem. 1985, 15, 945-950. Baldoli, C.; DelButtero, P.; Maiorana, S. Tetrahedron Lett. 1992, 33, 4049-52.
21. Mahaffy, C. A. L. Synth. React. Inorg. Met.-Org. Chem. 1985, 15, 945-950. Baldoli, C.; DelButtero, P.; Maiorana, S. Tetrahedron Lett. 1992, 33, 4049-52.
22. (a) Ohlsson, B.; Ullenius, C. J. Organomet. Chem. 1988, 350, 35.
23. (b) Ohlsson, B.; Ullenius, C.; Jagner, S.; Grivet, C.; Wenger, E.; Kundig, E. P. J. Organomet. Chem. 1989, 365, 243.
24. Tamura, S.; Takiguchi, C.; Sakai, K. J. Pharm. Soc. Jpn. 1956, 76, 915; Chem. Abstr. 1956, 51, 2782i.
25. Tamura, S.; Takiguchi, C.; Sakai, K. J. Pharm. Soc. Jpn. 1956, 76, 915; Chem. Abstr. 1956, 51, 2782i.
26. Semmelhack, M. F. Pure Appl. Chem. 1981, 53, 2379.
27. Walker, P. J. C.; Mawby, R. J. Inorg. Chim. Acta 1973, 7, 621.
28. Astruc, D. Tetrahedron, 1983, 39, 4027.
29. Semmelhack, M. F.; Clark, G. R.; Farina, R.; Saeman, M. J. Am. Chem. Soc. 1979, 101, 217.
30. 3. For a review of transition-metal-mediated dearomatization, see ref 14.
31. Card, R. J.; Trahanovsky, W. W. J. Org. Chem. 1980, 45, 2560.
32. Uemura, M.; Hayashi, Y.; Hayashi, Y. Tetrahedron Asymmetry 1994, 5, 1427.
33. Harman, W. D. Ph.D. Dissertation, Stanford University, 1987.
34. See ref Id (the kinetic 1,4-diene isomerizes under the Birch reduction reaction conditions).
35. 2 at -40 °C for compound 4).
36. Klopman, G. Chemical Reactivity and Reaction Paths; Wiley: New York, 1974; p 81. Extended Hückel calculations performed on a CAChe system in our laboratories show that N,N-dimethyl-p-toluidine has a larger HOMO coefficient at C(4) than at C(2), whereas, for the corresponding 5,6-dihydro compound, the electron density is more evenly distributed between these two reactive centers.
37. Coefficients for the highest energy occupied molecular orbital that is ring-centered (no. 38) for compound 1: C(4), 0.482; C(2), 0.389.
38. Bianchi, M.; Butti, A.; Christidis, Y.; Perronnet, J.; Barzaghi, F.; Cesana, R.; Nencioni, A. Eur. J. Med. Chem. 1988, 23, 45.
39. (a) Koga, W. Nippon Kagaku Zasshi 1956, 77, 1276.
40. (b) Webster, V. S.; Kamstra, L. D. Proc. S. Dakota Acad. Sci. 1951, 30, 40.
41. This statement holds for anisoles, phenols, and anilines without other's donor substituents.
42. Kopach, M. E.; Hpple, W. G.; Harman, W. D. J. Am. Chem. Soc. 1992, 114, 1786.
43. Kopach, M. E.; Harman, W. D. J. Aml. Chem. Soc. 1994, 115, 6581.
44. a,a = 0.36 V.
45. 3CN at 100 mV/s. The corresponding value for the parent 4H-anilinium snalog is estimated to be the same (Pigure 11).
46. Bard, A. J.; Faulkner, L. R. Electrochemical Methods. John Wiley & Sons: New York, 1989.
47. (a) Lay, P.; Magnuson, R.; Sen, J.; Taube, H. J. Am. Chem. Soc. 1982, 104, 7658.
48. (b) Lay, P. A.; Magnuson, P. H.; Taube, H. Inorg Synth. 1986, 24, 269.
49. Obtained in 938 yield from anibne (Calverly, M. J. Synth Commun. 1983, 13, 661); bp 63-64 C/O 15 Torr; Iit. bp 113-114 C/ 10 Torr.
50. -1 (Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Spectrometric Identification of Organic Compounds; Wiley: New York, 1981; p 121).
51. h/2 of about 20 Hz suggests these two methine resonances are axial when the cyclohexene ring is in a chair conformation (Jackman, L. M.; Sternhell, S. Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry; Pergamon Press: New York, 1969; p 288). H-(1) and H(4) were assigned using COSY and HETCOR experiments.
52. This amine stains red on TLC with Dragendorff's reagent: Touchstone, J. C.; Dobbins, M. F. Practice of Thin Layer Chromatography; Wiley & Sons: New York, 1978.