Efficient hydrogenation of sterically hindered olefins with borane-methyl sulfide complex

Journal of Organic Chemistry

Volumn 61, Issue 16, 1996, Pages 5246-5256

  Rathore, R ^a   Weigand, U ^a   Kochi, J K ^a  

^a University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0005831044     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960357e     Document Type: Article

References (79)

1. (a) Rylander, P. N. Catalytic Hydrogenation in Oragnic Synthesis; Academic Press: New York, 1979.
2. (b) Freifelder, M. Catalytic Hydrogenation in Oragnic Synthesis: Procedure and Commentary; Wiley: New York, 1978.
3. (c) Catalysis of Organic Reactions; Rylander, P. N., Greenfield, H., Augustine, R. L., Eds.; Marcel Dekker: New York, 1988.
4. (a) March, J. Advanced Organic Chemistry, 4th ed.; Wiley: New York, 1992, pp 713.
5. (b) Smith, M. B. Organic Synthesis; McGraw-Hill: New York, 1994; pp 430.
6. (a) Butler, D. N.; Gupta, I.; Ng, W. W.; Nyburg, S. C. J. Chem. Soc., Chem. Commun. 1980, 596.
7. (b) Bolze, R.; Eierdanz, H.; Schluter, K.; Massa, W.; Grahn, W.; Berndt, A. Angew. Chem., Int. Ed. Engl. 1982, 21, 924.
8. (c) Arnett, E. M.; Bollinger, J. M.; Sanda, J. C. J. Am. Chem. Soc. 1965, 87, 2050.
9. Catalytic hydrogenation of 2,3-bis(2,5-dimethoxy-4-methylphenyl)-bicyclo[2.2.2]oct-2-ene (1) in ethanol at 25°C in the presence of 10% palladium on charcoal or platinum catalyst resulted only traces of the hydrogenated product after 48 h.
10. Nelsen S. F.; Teasley, M. F. J. Org. Chem. 1988, 51, 3474. For other examples of ionic hydrogenation, see: Kursanov, D. N.; Parnes, Z. N.; Loim, N. M. Synthesis 1974, 633.
11. Nelsen S. F.; Teasley, M. F. J. Org. Chem. 1988, 51, 3474. For other examples of ionic hydrogenation, see: Kursanov, D. N.; Parnes, Z. N.; Loim, N. M. Synthesis 1974, 633.
12. Nelsen, D. J.; Cooper, P. J.; Soundararajan, R. J. Am. Chem. Soc. 1989, 111, 1414.
13. Mirafzal, G. A.; Bauld, N. L. J. Am. Chem. Soc. 1992, 114, 5457. Also see Mirafzal, G. A.; Liu, J.; Bauld, N. L. J. Am. Chem. Soc. 1993, 115, 6072.
14. Mirafzal, G. A.; Bauld, N. L. J. Am. Chem. Soc. 1992, 114, 5457. Also see Mirafzal, G. A.; Liu, J.; Bauld, N. L. J. Am. Chem. Soc. 1993, 115, 6072.
15. 7 was a demethylated compound which could not be identified.
16. Borane-methyl sulfide complex is available from Aldrich Chemical Co. and has been extensively utilized for the hydroboration of alkenes, see: Brown, H. C. Organic Synthesis Via Boranes; Wiley: New York, 1975.
17. Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60, 4399. Also see: Rathore, R.; Bosch, E.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2 1994, 1157.
18. Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60, 4399. Also see: Rathore, R.; Bosch, E.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2 1994, 1157.
19. Tolstikov, G. A.; Lerman, B. M.; Belogaeva, T. A. Synth. Commun. 1991, 21, 877.
20. Bosch, E.; Kochi, J. K. J. Am. Chem. Soc. 1996, 118, 1319.
21. Buckles, R. E.; Womer, W. D. J. Am. Chem. Soc. 1958, 80, 5055.
22. Baumstark, A. L.; McCloskey, C. J.; Witt, K. E. J. Org. Chem. 1978, 43, 3609. Also see: McMurry, J. E. Chem. Rev. 1989, 89, 1513 and references therein.
23. Baumstark, A. L.; McCloskey, C. J.; Witt, K. E. J. Org. Chem. 1978, 43, 3609. Also see: McMurry, J. E. Chem. Rev. 1989, 89, 1513 and references therein.
24. Komatsu, K.; Aonuma, S.; Jinbu, Y.; Tsuji, R.; Hirosawa, C.; Takeuchi, K. J. Org. Chem. 1991, 56, 196.
25. Kumada, K. Pure Appl. Chem. 1980, 52, 669 and references therein.
26. The hydrogenation of olefin 1 (in eq 1) with 1 equiv of the borane-methyl sulfide complex proceeded sluggishly with incomplete reduction. Since the boron-containing products were not identified, the complete stoichiometry in eq 1 was not established.
27. Sterically crowded olefins are known to resist hydroboration, see: Zweifel, G.; Brown, H. C. Org. React. 1963, 13, 1. Also see Butler et al. in ref 3.
28. Van Zorge, J. A.; Strating, J.; Wynberg, H. Recl. Trav. Chim. Pays-Bas 1970, 89, 781.
29. (a) Suzuki, H. Bull. Chem. Soc. Jpn. 1960, 33, 389.
30. (b) Suzuki, H.; Koyano, K.; Shida, T.; Kira, A. Bull. Chem. Soc. Jpn. 1979, 52, 2794.
31. Svanholm, U.; Jensen, B. S.; Parker, V. D. J. Chem. Soc., Perkin Trans. 2 1974, 907. Also see: Bard, A. J.; Phelps, J. J. Electroanal. Chem. 1970, 25, App. 2.
32. Svanholm, U.; Jensen, B. S.; Parker, V. D. J. Chem. Soc., Perkin Trans. 2 1974, 907. Also see: Bard, A. J.; Phelps, J. J. Electroanal. Chem. 1970, 25, App. 2.
33. (a) Mitchell, R. H.; Mazuch, L.; Shell, B.; West, P. R. Can. J. Chem. 1978, 56, 1246.
34. (b) Luh, T.-Y. Synth. Commun. 1981, 11, 829.
35. 2 (72%) and unidentified tetrahydro- and hexahydroacenaphthlenes (∼28%).
36. Bauld, N. L.; Yueh, W. J. Am. Chem. Soc. 1994, 116, 8845.
37. The reduction of olefins 2-4, 8, and 10 also indicated (by GC-MS analysis) the presence of a trace amount (<2%) of a second isomer of the hydrogenated product. In the case of olefin 1, the single isomer obtained was clearly identified by X-ray crystallography to be the cis isomer. However, the stereochemistry of the other hydrogenated alkanes in Table 1 is not known.
38. (a) Dodson, R. M.; Zielske, A. G. J. Org. Chem., 1967, 32, 28.
39. (b) Bauld, N. L.; Hudson, C. E. Tetrahedron Lett. 1974, 36, 3147 and references therein.
40. (a) Lopez, L.; Troisi, L. Tetrahedron Lett. 1989, 30, 3097.
41. (b) Ciminale, F.; Lopez, L.; Mele, G. Tetrahedron 1994, 50, 12685.
42. (c) Gassman, P. G.; Singleton, D. A. J. Am. Chem. Soc. 1984, 106, 7993.
43. (d) Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60, 7479 and references therein.
44. Although boron-containing products in eq 3 were not identified, the formation of alkane by the alternative sequence (involving hydroboration of alkene followed by protonolysis) is disfavored since it requires the presence of a carboxylic acid (such as propionic acid) and is usually carried out at elevated temperatures. See, Brown, H. C. in ref 9, pp 81.
45. Nelsen, S. F. Acc. Chem. Res. 1987, 20, 269.
46. Kim, E. K.; Kochi, J. K. J. Am. Chem. Soc. 1991, 113, 4962. Also see: Bandlish, B. K.; Shine, H. J. J. Org. Chem. 1977, 42, 561.
47. Kim, E. K.; Kochi, J. K. J. Am. Chem. Soc. 1991, 113, 4962. Also see: Bandlish, B. K.; Shine, H. J. J. Org. Chem. 1977, 42, 561.
48. + with zinc dust.
49. The complete stoichiometry in eq 6 was not established due to the difficulty in identifying boron-containing products.
50. (a) Freedman, H. H. In Carbonium Ions: Olah, G. A., Schleyer, P. v. R., Eds.; Wiley: New York, 1973; Vol. IV, p 1501.
51. (b) Olah, G. A.; Pittman, C. U., Jr. In Carbonium Ions; Olah, G. A., Schleyer, P. v. R., Eds.; Wiley: New York, 1968; Vol. I, p 153.
52. (c) Olah, G. A. Angew. Chem., Int. Ed. Engl. 1973, 12, 173.
53. (d) Deno, N. C; Jaruzelski, J. J.; Schreisheim, A. J. Am. Chem. Soc. 1955, 77, 3044.
54. (a) Al-Ekabi, H.; Kawata, H.; de Mayo, P. J. Org. Chem. 1988, 53, 1471.
55. (b) Azarani, A.; Berinstain, A. B.; Johnston, L. J.; Kazanis, S. J. Photochem. Photobiol. A: Chem. 1991, 57, 175 and references therein.
56. Similar yields of hydrogenated alkanes were obtained with tris(4-bromophenyl)aminium hexachloroantimonate ("magic blue") as the one-electron oxidant.
57. (a) Baban, J. A.; Roberts, B. P. J. Chem. Soc., Perkin Trans. 2 1987, 497.
58. (b) Paul, V.; Roberts, B. P. J. Chem. Soc., Perkin Trans. 2 1988, 1183.
59. (c) Baban, J. A.; Roberts, B. P. J. Chem. Soc., Perkin Trans. 2 1988, 1195. See also: Lucarini, M.; Pedulli, G. F.; Valgimigli, L. J. Org. Chem. 1996, 61, 1161.
60. (c) Baban, J. A.; Roberts, B. P. J. Chem. Soc., Perkin Trans. 2 1988, 1195. See also: Lucarini, M.; Pedulli, G. F.; Valgimigli, L. J. Org. Chem. 1996, 61, 1161.
61. The formulation in eqs 10 and 11 does account for the hydrogenation of both olefin cation radicals and carbocations with borane to form the corresponding alkanes. However, the fate of the boron-containing products could not be identified, and thus eqs 10 and 11 may merely represent a simplified scheme for a rather complex reaction.
62. (a) Johnston, L. J.; Kanigan, T. J. Am. Chem. Soc. 1990, 112, 1271.
63. (b) Hart, H.; Teuerstein, A.; Babin, M. A. J. Am. Chem. Soc. 1981, 103, 903.
64. (c) Eberson, L.; Radner, F. Acta Chem. Scand. 1991, 45, 1093 and references therein.
65. (d) Also see Al-Ekabi et al. in ref 34.
66. McMurry, J. E.; Fleming, M. P. J. Am. Chem. Soc. 1974, 96, 4708.
67. Hunt, S. E.; Lindsey, A. S. J. Chem. Soc. (C) 1968, 3049.
68. (a) McHale, D.; Mamalis, P.; Green, J.; Marcinkiewicz, S. J. Chem. Soc. 1958, 1600.
69. Smith, L. I.; Nichols, J. J. Org. Chem. 1941, 6, 489.
70. Moser, R. E.; Cassidy, H. G. J. Org. Chem. 1965, 30, 2602.
71. (a) Bachmann, W. E.; Chu, E. J.-W. J. Am. Chem. Soc. 1936, 58, 1181.
72. (b) Letsinger, R. L.; Lansbury, P. T. J. Am. Chem. Soc. 1935, 55, 3837.
73. Longone, D. T.; Simanyi, L. H. J. Org. Chem. 1964, 29, 3245.
74. Staab, H. A.; Herz, C. P.; Henke, H. E. Chem. Ber. 1971, 110, 3351.
75. Burckhalter, J. H.; Sam, J. J. Am. Chem. Soc. 1952, 74, 187.
76. Perrier, S.; Sankararaman, S.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2 1993, 825.
77. Bosch, E.; Rathore, R.; Kochi, J. K. J. Org. Chem. 1994, 59, 2529.
78. 51
79. Lucarini, M.; Pedulli, F. P.; Alberti, A.; Paradisi, C.; Roffia, S. J. Chem. Soc., Perkin Trans. 2 1993, 2083.