A desilylation and a one-pot desilylation-oxidation of aliphatic tert-butyldimethylsilyl ethers using catalytic quantities of PdCl2(CH3CN)2

Journal of Organic Chemistry

Volumn 61, Issue 9, 1996, Pages 2918-2919

  Wilson, Noel S ^a   Keay, Brian A ^a  

^a UNIVERSITY OF CALGARY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000909963     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo952210d     Document Type: Article

References (32)

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9. For examples of two-step desilylation-oxidation sequences, see: (a) Sames, D.; Polt, R. J. Org. Chem. 1994, 59, 4596. (b) Angle, S. R.; Frutos, R. P. J. Org. Chem. 1993, 58, 5135. (c) Wild, H. J. Org. Chem. 1994, 59, 2748.
10. For examples of two-step desilylation-oxidation sequences, see: (a) Sames, D.; Polt, R. J. Org. Chem. 1994, 59, 4596. (b) Angle, S. R.; Frutos, R. P. J. Org. Chem. 1993, 58, 5135. (c) Wild, H. J. Org. Chem. 1994, 59, 2748.
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17. For other oxidations of alcohols involving palladium catalysts, see: (a) Berzelus, J. J. Ann. 1828, 13, 435. (b) Lloyd, W. G. J. Org. Chem. 1967, 32, 2816. (c) Blackburn, T. F.; Schwartz, J J Chem. Soc., Chem. Commun. 1977, 157. (d) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 4387. (e) Nagashima, H.; Tsuji, J. Tetrahedron 1985, 41, 5645. (f) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. Bull. Chem. Soc. Jpn. 1990, 63, 255. (g) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Chem. Soc., Chem. Commun. 1989, 1072. (h) Benhaddou, R.; Czernecki, S.; Ville, G.; Zegar, A. Organometallics 1988, 7, 2435. (i) Bellosta, V.; Benhaddou, R., Czernecki, S. Synlett 1993, 861.
18. For other oxidations of alcohols involving palladium catalysts, see: (a) Berzelus, J. J. Ann. 1828, 13, 435. (b) Lloyd, W. G. J. Org. Chem. 1967, 32, 2816. (c) Blackburn, T. F.; Schwartz, J J Chem. Soc., Chem. Commun. 1977, 157. (d) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 4387. (e) Nagashima, H.; Tsuji, J. Tetrahedron 1985, 41, 5645. (f) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. Bull. Chem. Soc. Jpn. 1990, 63, 255. (g) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Chem. Soc., Chem. Commun. 1989, 1072. (h) Benhaddou, R.; Czernecki, S.; Ville, G.; Zegar, A. Organometallics 1988, 7, 2435. (i) Bellosta, V.; Benhaddou, R., Czernecki, S. Synlett 1993, 861.
19. For other oxidations of alcohols involving palladium catalysts, see: (a) Berzelus, J. J. Ann. 1828, 13, 435. (b) Lloyd, W. G. J. Org. Chem. 1967, 32, 2816. (c) Blackburn, T. F.; Schwartz, J J Chem. Soc., Chem. Commun. 1977, 157. (d) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 4387. (e) Nagashima, H.; Tsuji, J. Tetrahedron 1985, 41, 5645. (f) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. Bull. Chem. Soc. Jpn. 1990, 63, 255. (g) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Chem. Soc., Chem. Commun. 1989, 1072. (h) Benhaddou, R.; Czernecki, S.; Ville, G.; Zegar, A. Organometallics 1988, 7, 2435. (i) Bellosta, V.; Benhaddou, R., Czernecki, S. Synlett 1993, 861.
20. For other oxidations of alcohols involving palladium catalysts, see: (a) Berzelus, J. J. Ann. 1828, 13, 435. (b) Lloyd, W. G. J. Org. Chem. 1967, 32, 2816. (c) Blackburn, T. F.; Schwartz, J J Chem. Soc., Chem. Commun. 1977, 157. (d) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 4387. (e) Nagashima, H.; Tsuji, J. Tetrahedron 1985, 41, 5645. (f) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. Bull. Chem. Soc. Jpn. 1990, 63, 255. (g) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Chem. Soc., Chem. Commun. 1989, 1072. (h) Benhaddou, R.; Czernecki, S.; Ville, G.; Zegar, A. Organometallics 1988, 7, 2435. (i) Bellosta, V.; Benhaddou, R., Czernecki, S. Synlett 1993, 861.
21. For other oxidations of alcohols involving palladium catalysts, see: (a) Berzelus, J. J. Ann. 1828, 13, 435. (b) Lloyd, W. G. J. Org. Chem. 1967, 32, 2816. (c) Blackburn, T. F.; Schwartz, J J Chem. Soc., Chem. Commun. 1977, 157. (d) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 4387. (e) Nagashima, H.; Tsuji, J. Tetrahedron 1985, 41, 5645. (f) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. Bull. Chem. Soc. Jpn. 1990, 63, 255. (g) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Chem. Soc., Chem. Commun. 1989, 1072. (h) Benhaddou, R.; Czernecki, S.; Ville, G.; Zegar, A. Organometallics 1988, 7, 2435. (i) Bellosta, V.; Benhaddou, R., Czernecki, S. Synlett 1993, 861.
22. For other oxidations of alcohols involving palladium catalysts, see: (a) Berzelus, J. J. Ann. 1828, 13, 435. (b) Lloyd, W. G. J. Org. Chem. 1967, 32, 2816. (c) Blackburn, T. F.; Schwartz, J J Chem. Soc., Chem. Commun. 1977, 157. (d) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 4387. (e) Nagashima, H.; Tsuji, J. Tetrahedron 1985, 41, 5645. (f) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. Bull. Chem. Soc. Jpn. 1990, 63, 255. (g) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Chem. Soc., Chem. Commun. 1989, 1072. (h) Benhaddou, R.; Czernecki, S.; Ville, G.; Zegar, A. Organometallics 1988, 7, 2435. (i) Bellosta, V.; Benhaddou, R., Czernecki, S. Synlett 1993, 861.
23. For other oxidations of alcohols involving palladium catalysts, see: (a) Berzelus, J. J. Ann. 1828, 13, 435. (b) Lloyd, W. G. J. Org. Chem. 1967, 32, 2816. (c) Blackburn, T. F.; Schwartz, J J Chem. Soc., Chem. Commun. 1977, 157. (d) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 4387. (e) Nagashima, H.; Tsuji, J. Tetrahedron 1985, 41, 5645. (f) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. Bull. Chem. Soc. Jpn. 1990, 63, 255. (g) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Chem. Soc., Chem. Commun. 1989, 1072. (h) Benhaddou, R.; Czernecki, S.; Ville, G.; Zegar, A. Organometallics 1988, 7, 2435. (i) Bellosta, V.; Benhaddou, R., Czernecki, S. Synlett 1993, 861.
24. For other oxidations of alcohols involving palladium catalysts, see: (a) Berzelus, J. J. Ann. 1828, 13, 435. (b) Lloyd, W. G. J. Org. Chem. 1967, 32, 2816. (c) Blackburn, T. F.; Schwartz, J J Chem. Soc., Chem. Commun. 1977, 157. (d) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 4387. (e) Nagashima, H.; Tsuji, J. Tetrahedron 1985, 41, 5645. (f) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. Bull. Chem. Soc. Jpn. 1990, 63, 255. (g) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Chem. Soc., Chem. Commun. 1989, 1072. (h) Benhaddou, R.; Czernecki, S.; Ville, G.; Zegar, A. Organometallics 1988, 7, 2435. (i) Bellosta, V.; Benhaddou, R., Czernecki, S. Synlett 1993, 861.
25. For other oxidations of alcohols involving palladium catalysts, see: (a) Berzelus, J. J. Ann. 1828, 13, 435. (b) Lloyd, W. G. J. Org. Chem. 1967, 32, 2816. (c) Blackburn, T. F.; Schwartz, J J Chem. Soc., Chem. Commun. 1977, 157. (d) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 4387. (e) Nagashima, H.; Tsuji, J. Tetrahedron 1985, 41, 5645. (f) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. Bull. Chem. Soc. Jpn. 1990, 63, 255. (g) Baba, T.; Kameta, K.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Chem. Soc., Chem. Commun. 1989, 1072. (h) Benhaddou, R.; Czernecki, S.; Ville, G.; Zegar, A. Organometallics 1988, 7, 2435. (i) Bellosta, V.; Benhaddou, R., Czernecki, S. Synlett 1993, 861.
26. 2SiOH by GC/MS.
27. 11 emphasized that anhydrous conditions were necessary for the oxidation, we felt at the time that if the oxidation would proceed in wet DMF then the desilylation might also be possible in wet DMF. To our delight, the oxidation of 6 to 7 proceeded smoothly in DMF containing 5 equiv of water.
28. At this time, we do not understand why the mixed solvent system works so well. For material on the use of and effects of mixed solvents with other systems, see: (a) Ta-Shma, R.; Rappoport Z. Adv. Phys. Org. Chem. 1992, 27, 239. (b) Watts, D. W. In Physical Chemistry of Organic Solvent Systems; Covington, A. V., Dickinson, T., Eds.; Plenum Press: New York, 1973; pp 715-716.
29. At this time, we do not understand why the mixed solvent system works so well. For material on the use of and effects of mixed solvents with other systems, see: (a) Ta-Shma, R.; Rappoport Z. Adv. Phys. Org. Chem. 1992, 27, 239. (b) Watts, D. W. In Physical Chemistry of Organic Solvent Systems; Covington, A. V., Dickinson, T., Eds.; Plenum Press: New York, 1973; pp 715-716.
30. 2 (5.5 mg, 21 μmol). The reaction mixture was refluxed (75°C) for 6 h (followed by GC) and cooled to rt and the acetone removed in vacuo to leave an oil. Purification by distillation provided 1-phenyl-1-ethanol (90%).
31. 4) and removed in vacuo to leave an oil which was distilled to provide acetophenone (94%).
32. Presumably, the palladium(O) catalyst oxidatively inserts into the aryl-bromine bond in both 2-bromomestilyene and the substrate resulting in debrominated product. Most likely, aryl iodides would be removed under similar conditions.