O-TBS-N-tosylhydroxylamine: A reagent for facile conversion of alcohols to oximes

Organic Letters

Volumn 10, Issue 11, 2008, Pages 2259-2261

  Kitahara, Katsushi ^a   Toma, Tatsuya ^a   Shimokawa, Jun ^a   Fukuyama, Tohru ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; CESIUM; CESIUM FLUORIDE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; FLUORIDE; OXIME; TOLUENESULFONIC ACID DERIVATIVE;

ARTICLE; CHEMISTRY;

ALCOHOLS; CESIUM; FLUORIDES; INDICATORS AND REAGENTS; OXIMES; TOSYL COMPOUNDS;

EID: 52649144371     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol800677p     Document Type: Article

References (22)

1. For a review, see: Yamane, M.; Narasaka, K. In Science of Synthesis; Padwa, A., Ed.; Georg Thieme Verlag: Stuttgart, 2004; Vol. 27, pp 605-647.
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4. Toma, T.; Shimokawa, J.; Fukuyama, T. Org. Lett. 2007, 9, 3195.
5. Mitsunobu, O. Synthesis 1981, 1.
6. An N-arylsulfonyl hydroxylamine derivative is known as an excellent substrate for Mitsunobu reaction: Yamashita, T.; Kawai, N.; Tokuyama, H.; Fukuyama, T. J. Am. Chem. Soc. 2005, 127, 15038.
7. (a) Similar substitution reactions using hydroxylamine derivatives are known: Maurer, P. J.; Miller, M. J. J. Am. Chem. Soc. 1982, 104, 3096.
8. (b) Hanessian, S.; Yang, R.-Y. Synlett 1995, 633.
9. (c) Knight, D. W.; Leese, M. P. Tetrahedron Lett. 2001, 42, 2593.
10. For other reports of O-silyl-N-sulfonylhydroxylamines, see: (a) Bruynes, C. A.; Jurriens, T. K. J. Org. Chem. 1982, 47, 3966.
11. (b) Pohlman, G.; Brink, K.; Bliefert, C. Z. Naturforsch., B: Anorganische Chemie, Organische Chemie 1980, 35B, 1494.
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13. For experimental details, see: Supporting Information.
14. While several fluoride sources including TBAF were examined, CsF gave the best result.
15. Enev, V. S.; Drescher, M.; Kählig, H.; Mulzer, J. Synlett 2005, 2227. According to the authors, this was the first example of a stereoselective synthesis of cis-α,β-unsaturated oxime.
16. Since aldehydes react with TsNHOTBS to give silylated hydroxamic acids presumably by the mechanism similar to Angeli-Rimini's reaction, they are not compatible with the present method. For Angeli-Rimini's reaction, see: (a) Hassner, A.; Wiederkehr, R.; Kascheres, A. J. J. Org. Chem. 1970, 35, 1962.
17. (b) Porcheddu, A.; Giacomelli, G. J. Org. Chem. 2006, 71, 7057.
18. (a) Pearson, D. E.; Keaton, O. D. J. Org. Chem. 1963, 28, 1557.
19. (b) Greer, F.; Pearson, D. E. J. Am. Chem. Soc. 1955, 77, 6649.
20. Excess alcohols were used in these cases because the hydroxylamine intermediates have similar polarity to 5 and could not be isolated in pure form. From the synthetic point of view, an excess amount of 5 could be used if it is not necessary to isolate the intermediate in pure form, because 5 decomposes upon treatment with CsF.
21. 3 substantialy decreases the efficiency of the elimination of toluenesulfinate, often resulting in incomplete reactions.
22. A one-pot procedure was employed because partial desilylation was observed in the first step.