Catalytic epoxidation of hindered olefins with dioxygen. Fast oxygen atom transfer to olefin cation radicals from nitrogen oxides

Journal of the American Chemical Society

Volumn 118, Issue 6, 1996, Pages 1319-1329

  Bosch, Eric ^a   Kochi, Jay K ^a  

^a University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EPOXIDE;

ARTICLE; CATALYSIS; CYCLIC POTENTIOMETRY; DRUG STABILITY; ELECTRON TRANSPORT; EPOXIDATION; INFRARED SPECTROPHOTOMETRY; PHOTOCHEMISTRY; REACTION ANALYSIS; SPECTROPHOTOMETRY; TEMPERATURE;

EID: 0029875368     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja953786n     Document Type: Article

References (100)

1. Weast, R. C., Lide, D. R. Eds. Handbook of Chemistry and Physics, 70th ed.; CRC Press: Boca Raton, FL. 1989.
2. (a) Charterjee, J.; Coombes, R. G.; Barnes, J. R.; Fildes, M. J. J. Chem. Soc., Perkin Trans. 2 1995, 1031.
3. (b) Shechter, H. Rec. Chem. Prog. 1964, 25, 55.
4. (c) Reibsomer, J. L. Chem. Rev. 1945, 36, 157.
5. (d) Bonetti, G. A.; de Savigny, C. B.; Michalski, G.; Rosenthal, R. J. Org. Chem. 1968, 33, 237.
6. (e) Wilkes, J. B.; Wall, R. G. J. Org. Chem. 1980, 45, 247.
7. Larson, H. O. In The Chemistry of the Nitro and Nitroso Groups: Feuer, H., Ed.; Interscience: New York, 1969; pp 319 ff.
8. (a) Pryor, W. A.; Lightsey, J. W.; Church, D. F. J. Am. Chem. Soc. 1982, 104, 6685.
9. (b) Giamalva, D. H.; Kenion, G. B.; Church, D. F.; Pryor, W. A. J. Am. Chem. Soc. 1987, 109, 7059.
10. Brand, J. C. D.; Stevens, I. D. R. J. Chem. Soc. 1958, 629.
11. (a) Jaffe, S.; Keith, J. J. Chem. Phys. 1968, 48, 2805.
12. (b) Jaffe, S.; Grant, R. C. S. J. Chem. Phys. 1969, 50, 3477.
13. Nojima, K.; Ohya, T.; Kanno, S.; Hirobe, M. Chem. Pharm. Bull. 1982, 30, 4500.
14. (a) Nakata, M.; Frei, H. J. Am. Chem. Soc. 1989, 111, 5240.
15. (b) Nakata, M.; Frei, H. J. Phys. Chem. 1989, 93, 7670.
16. (c) Fitzmaurice, D. J.; Frei, H. J. Phys. Chem. 1992, 96, 10308.
17. (d) Blatter, F.; Frei, H. J. Phys. Chem. 1993, 97, 1178.
18. (e) Frei, H. Chimia 1991, 45, 175.
19. See also: (a) Loison, J. C.; Dedonder-Lardeux, C.; Jouvet, C.; Solgadi, D. J. Phys. Chem. 1991, 95, 9192. (b) Tanaka, N.; Kajii, Y.; Shibuya, K.; Nakata, M. J. Phys. Chem. 1993, 97, 7048.
20. See also: (a) Loison, J. C.; Dedonder-Lardeux, C.; Jouvet, C.; Solgadi, D. J. Phys. Chem. 1991, 95, 9192. (b) Tanaka, N.; Kajii, Y.; Shibuya, K.; Nakata, M. J. Phys. Chem. 1993, 97, 7048.
21. Bosch, E.; Kochi, J. K. J. Chem. Soc., Chem. Commun. 1993, 667.
22. (a) Traylor, T. G.; Miksztal, A. R. J. Am. Chem. Soc. 1987, 109, 2770.
23. (b) Traylor, T. G.; Xu, F. J. Am. Chem. Soc. 1988, 110, 1953.
24. (c) He, G.-X.; Arasasingham, R. D.; Zhang, G.-H.; Bruice, T. C. J. Am. Chem. Soc. 1991, 113, 9828. See also: Kim, T.; Mirafzal, G. A.; Liu, J.; Bauld, N. L. J. Am. Chem. Soc. 1993, 115, 7653.
25. (c) He, G.-X.; Arasasingham, R. D.; Zhang, G.-H.; Bruice, T. C. J. Am. Chem. Soc. 1991, 113, 9828. See also: Kim, T.; Mirafzal, G. A.; Liu, J.; Bauld, N. L. J. Am. Chem. Soc. 1993, 115, 7653.
26. Bauld, N. L.; Mirafzal, G. A. J. Am. Chem. Soc. 1991, 113, 3613.
27. (a) Belluci, G.; Bianchini, R.; Chiappe, C.; Marioni, F.; Ambrosetti, R.; Brown, R. S.; Slebocka-Tilk, H. J. Am. Chem. Soc. 1989, 111, 2640.
28. (b) Nugent, W. A. J. Org. Chem. 1980, 45, 453.
29. (c) Garratt, D. G. Tetrahedron Lett. 1978, 1915.
30. (d) Olah, G. A.; Schilling, P.; Westerman, P. W.; Lin, H. C. J. Am. Chem. Soc. 1974, 96, 3581.
31. (e) Wieringa, J. H.; Strating J.; Wynberg, H. Tetrahedron Lett. 1970, 4579.
32. (f) Strating, J.; Wieringa, J. H.; Wynberg, H. J. Chem. Soc., Chem. Commun. 1969, 907. Note that the allylic hydrogens in olefins 1-5 are coplanar with the olefin and are thus not susceptible to abstraction or deprotonation (see: Nelsen, S. F. Acc. Chem. Res. 1987, 20, 269).
33. (f) Strating, J.; Wieringa, J. H.; Wynberg, H. J. Chem. Soc., Chem. Commun. 1969, 907. Note that the allylic hydrogens in olefins 1-5 are coplanar with the olefin and are thus not susceptible to abstraction or deprotonation (see: Nelsen, S. F. Acc. Chem. Res. 1987, 20, 269).
34. The aromatic rings are tilted with respect to the central double bond sufficient to cause tetraarylethylenes to be severely hindered. (a) Suzuki, H. Bull. Chem. Soc. Jpn. 1960, 33, 389. (b) Suzuki, H.; Koyano, K.; Shida, T.; Kira, A. Bull. Chem. Soc. Jpn. 1979, 52, 2794. See also: Bock, H.; Nather, C.; Havlas, Z. J. Chem. Soc., Chem. Commun. 1995, 1111.
35. The aromatic rings are tilted with respect to the central double bond sufficient to cause tetraarylethylenes to be severely hindered. (a) Suzuki, H. Bull. Chem. Soc. Jpn. 1960, 33, 389. (b) Suzuki, H.; Koyano, K.; Shida, T.; Kira, A. Bull. Chem. Soc. Jpn. 1979, 52, 2794. See also: Bock, H.; Nather, C.; Havlas, Z. J. Chem. Soc., Chem. Commun. 1995, 1111.
36. The aromatic rings are tilted with respect to the central double bond sufficient to cause tetraarylethylenes to be severely hindered. (a) Suzuki, H. Bull. Chem. Soc. Jpn. 1960, 33, 389. (b) Suzuki, H.; Koyano, K.; Shida, T.; Kira, A. Bull. Chem. Soc. Jpn. 1979, 52, 2794. See also: Bock, H.; Nather, C.; Havlas, Z. J. Chem. Soc., Chem. Commun. 1995, 1111.
37. 4) which coexist in a highly mobile equilibrium.
38. (a) Marmo, F. F. J. Opt. Soc. Am. 1953, 43, 1186.
39. (b) Fateley, W. G.; Bent, H. A.; Crawford, B., Jr. J. Chem. Phys. 1959, 31, 204.
40. (c) Keck, D. B., Hause, C. D. J. Mol. Spectrosc. 1980, 27, 465.
41. 2, see: Bosch, E.; Kochi, J. K. J. Org. Chem. 1994, 59, 3314.
42. See also: Shida, T. Electronic Absorption Spectra of Radical Ions, Elsevier: New York, 1988.
43. Smith, J. H. J. Am. Chem. Soc. 1943, 65, 74.
44. Laane, J.; Ohlsen, J. R. Prog. Inorg. Chem. 1980, 27, 465.
45. Schmidt, W.; Steckhan, E. Chem. Ber. 1980, 113, 577. See also: Bell, F. A.; Ledwith, A.; Sherrington, D. C. J. Chem. Soc. C 1969, 2719.
46. Schmidt, W.; Steckhan, E. Chem. Ber. 1980, 113, 577. See also: Bell, F. A.; Ledwith, A.; Sherrington, D. C. J. Chem. Soc. C 1969, 2719.
47. 2. See: (a) Shaw, A. W.; Vosper, A. J. J. Chem. Soc., Dalton Trans. 1959, 31, 204. (b) Ashmore, P. G.; Tyler, B. J. Chem. Soc. 1961, 1017.
48. 2. See: (a) Shaw, A. W.; Vosper, A. J. J. Chem. Soc., Dalton Trans. 1959, 31, 204. (b) Ashmore, P. G.; Tyler, B. J. Chem. Soc. 1961, 1017.
49. Nelsen, S. F.; Teasley, M. F.; Kapp, D. L.; Kessel, C. R.; Grezzo, L. A. J. Am. Chem. Soc. 1984, 106, 791.
50. 13d reported the exclusive formation of ketone 14 on reaction of 1 with nitryl cation, but they did not detect epoxide 12.
51. + (Compare Lopez et al. in ref 31).
52. Masnovi, J. M.; Kochi, J. K.; Hilinski, E. R.; Rentzepis, P. M. J. Am. Chem. Soc. 1986, 108, 1126.
53. (a) Masnovi, J. M., Kochi, J. K. Recl. Trav. Chim. Pays-Bas 1986, 105, 286.
54. (b) Rathore, R.; Kochi, J. K. J. Org. Chem., in press.
55. (c) Bosch, E.; Kochi, J. K. Res. Chem. Intermed., in press.
56. Bielski, B. H. J.; Allen, A. O. J. Phys. Chem. 1967, 71, 4544.
57. .+ decolorized, and 3,6-dimethyl-9,10-bis(4′-methylphenyl)phenamhrene was formed.
58. .+ were performed at -5 to +10°C since the cation radical was persistent in the presence of nitrogen oxides at -78°C.
59. + = bis(triphenylphosphoranylidene)ammonium prepared according to Ruff, J. K.; Schlientz, W. J. Inorg. Synth. 1974, 15, 84.
60. 32
61. (a) Lopez, L.; Troisi, L. Tetrahedron Lett. 1989, 30, 3097
62. (b) Lopez, L.; Mele, G.; Finandanese, V.; Cardellicchio, C.; Nacci, A. Tetrahedron 1994, 50, 9097.
63. The reaction was heterogeneous since nitrosonium salts are only sparingly soluble in dichloromethane.
64. The epoxides were also rapidly isomerized to the corresponding ketones during cyclic voltammetric measurements as described in the Experimental Section. For the electron-transfer chain isomerization at the electrode during cyclic voltammetric studies, see: Lebouc, A.; Tallee, A.; Simonet, J. J. Chem. Soc., Chem. Commun. 1982, 387, Uneyama, K.; Isimura, A.; Fujii, K.; Torri, S. Tetrahedron Lett. 1983, 24, 2857.
65. The epoxides were also rapidly isomerized to the corresponding ketones during cyclic voltammetric measurements as described in the Experimental Section. For the electron-transfer chain isomerization at the electrode during cyclic voltammetric studies, see: Lebouc, A.; Tallee, A.; Simonet, J. J. Chem. Soc., Chem. Commun. 1982, 387, Uneyama, K.; Isimura, A.; Fujii, K.; Torri, S. Tetrahedron Lett. 1983, 24, 2857.
66. (a) Compare: Groves, J. T.; Quinn, R. J. Am. Chem. Soc. 1985, 107, 5790. See also Groves, J. T.; Stern, M. K. J. Am. Chem. Soc. 1987, 109, 3812.
67. (a) Compare: Groves, J. T.; Quinn, R. J. Am. Chem. Soc. 1985, 107, 5790. See also Groves, J. T.; Stern, M. K. J. Am. Chem. Soc. 1987, 109, 3812.
68. (b) For a review, see: Sheldon, R. A.; Kochi, J. K. Metal-Catalyzed Oxidations of Organic Compounds: Academic: New York, 1981.
69. Indeed, the least hindered olefin in this study, isopropylideneadamantane 6, yielded a complex mixture of products which did not include the epoxide. Note that the allylic hydrogen atoms of 6 are susceptible to abstraction/deprotonation. See: Nelsen, S. F.; Kapp, D. L.; Teasley, M. F. J. Org. Chem. 1984, 49, 579.
70. Eberson, L.; Radner, F. Acta Chem. Scand., Sect. B 1985, 39, 343.
71. (a) James, D. W.; Marshall, R. C. J. Phys. Chem. 1968, 72, 2963.
72. (b) Redmond, T. F.; Wayland, B. B. J. Phys. Chem. 1968, 72, 1626.
73. (c) Brunning, J.; Frost, M. J.; Smith, I. W. M. Int. J. Chem. Kinet. 1988, 20, 957.
74. (d) Vosper, A. J. J. Chem Soc. A 1970, 2191.
75. Pinnick, D. A.; Agnew, S. F.; Swanson, B. I. J. Phys. Chem. 1992, 96, 7092.
76. (a) Parts, L.; Miller, J. T., Jr. J. Chem. Phys. 1965, 43, 136.
77. (b) Givan, A.; Loewenschuss, A. J. Chem. Phys. 1991, 94, 7562.
78. (a) Bontempelli, G.; Mazzochin, G.-A.; Magno, F. Electroanal. Chem. Interfacial Electrochem. 1974, 55, 91.
79. (b) Wartel, A.; Boughriet, A.; Fischer, J. C. Anal. Chim. Acta 1979, 19, 811.
80. Bosch, E.; Kochi, J. K. Res. Chem. Intermed. 1993, 19, 811.
81. 2 with olefins in nonpolar solvents such as carbon tetrachloride and cyclohexane proceeds via a radical (addition) mechanism. See Chatterjee et al. in ref 2a. Shechter in ref 2b, and Pry or in ref 4.
82. Lee, K. Y.; Kuchynka, D. J.; Kochi, J. K. Inorg. Chem. 1990, 29, 4196.
83. Nelsen, S. F.; Akaba, R. J. Am. Chem. Soc. 1981, 103, 2096. See also: Nelsen, S. F. Acc. Chem. Res. 1987, 20, 269.
84. Nelsen, S. F.; Akaba, R. J. Am. Chem. Soc. 1981, 103, 2096. See also: Nelsen, S. F. Acc. Chem. Res. 1987, 20, 269.
85. 3 is presumably the other product of the photolysis, but the nature or subsequent reactivity of this ion pair is not known. However, any nitrosonium cation thus formed can intervene in the reaction pathway.
86. 2, but we do not intend to exclude the direct involvement of nitrate.
87. +] is favored. See: Rathore, R.; Bosch, E.; Kochi, J. K. Tetrahedron 1994, 50, 6722. Note that the temperature dependence of the preequilibrium disproportionation in eq 35 is expected to follow the reverse trend (compare Bosch, E.; Kochi, J. K. J. Org. Chem. 1994, 59, 3314).
88. +] is favored. See: Rathore, R.; Bosch, E.; Kochi, J. K. Tetrahedron 1994, 50, 6722. Note that the temperature dependence of the preequilibrium disproportionation in eq 35 is expected to follow the reverse trend (compare Bosch, E.; Kochi, J. K. J. Org. Chem. 1994, 59, 3314).
89. (a) Ingold, K. U. In Free Radicals; Kochi, J. K., Ed.; Wiley: New York 1973; Vol. 1, pp 37 ff.
90. - in eqs 25 and 26 also bear a strong parallel to the paramagnetic behavior of alkyl radicals (R.) in bimolecular coupling (R-R) and disproportionation [RH + R(-H)] with uniformly low activation barriers (see: Benson, S. W. Adv. Photochem. 1964, 2, 1).
91. For examples of concerted and stepwise atom transfers in free radical chemistry, see: Ingold, K. U.; Roberts, B. P. Free-Radical Substitution Reactions; Wiley: New York 1971.
92. 2 is likely to be a multistep process, the reviewer has suggested that an intermediate peroxynitrite radical (.OONO) may also enter separately into the catalytic chain process in Scheme 3 in indeterminant amounts. Compare the epoxidation of olefins by alkylperoxy radicals. Marnett, L. J. Carcinogenesis 1987, 8, 1365. See also: Mayo, F. R. Acc. Chem. Res. 1968, 1, 193.
93. 2 is likely to be a multistep process, the reviewer has suggested that an intermediate peroxynitrite radical (.OONO) may also enter separately into the catalytic chain process in Scheme 3 in indeterminant amounts. Compare the epoxidation of olefins by alkylperoxy radicals. Marnett, L. J. Carcinogenesis 1987, 8, 1365. See also: Mayo, F. R. Acc. Chem. Res. 1968, 1, 193.
94. The cation radical catalyzed chain oxygenation of adamantylideneadamantane with dioxygen has been reported by Nelsen et al. in ref 45 to yield adamantylideneadamantane-dioxetane. In oxygenations catalyzed by nitrosonium and nitryl salts, these authors found adamantylideneadamantane oxide to be the major (isolated) product. They suggested that epoxide was formed by a nitrosonium-catalyzed decomposition of the dioxetane. However, we believe that the epoxide formed during the oxygenations induced by nitrosonium can be ascribed to eq 37. We further note that the reaction of adamantylideneadamatane cation radical with dioxygen is generally competitive with its reaction with either nitrogen dioxide or nitrate. Since the competition (quantitatively) will be a function of the respective concentrations of reactants, the absolute rates of reactions and the reversibile nature of the reactions cannot be evaluated at this juncture.
95. 54 is difficult to risorously delineate. See: Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60, 7479.
96. The acid-catalyzed pinacol rearrangement of epoxides, in particular adamamtylideneadamamane oxide, is well known (see: Wynberg, H.; Boelema, E.; Wieringa, J. H.; Strating, J. Tetrahedron Lett. 1970, 3613).
97. The low conversions (<5%) observed in the control reactions may have occurred adventitiously during workup.
98. Elsenhaumer, R. L. J. Org. Chem. 1988, 53, 437.
99. Depovere, P.; Devis, R. Bull. Chim. Soc. Fr. 1968, 2470.
100. Bandlish, B. K.; Shine, H. J. J. Org. Chem. 1977, 42, 561.