Selective cleavage of primary MPM ethers with TMSI/Et3N

Tetrahedron Letters

Volumn 50, Issue 31, 2009, Pages 4552-4553

  Kadota, Isao ^a   Yamagami, Yuji ^a   Fujita, Naoya ^a   Takamura, Hiroyoshi ^a  

^a OKAYAMA UNIVERSITY   (Japan)

Author keywords

Deprotection; MPM ether; Selective cleavage; TMSI

Indexed keywords

BENZYLIDENEACETONE; ETHER DERIVATIVE; METHOXYPHENYL METHYL ETHER; SILANE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; SYNTHESIS;

EID: 66949118252     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2009.05.084     Document Type: Article

References (12)

1. Wuts P.G.M., and Greene T.W. Protective Groups in Organic Synthesis. 4th ed. (2007), John Wiley & Sons, New Jersey 121-130
2. Kadota I., Ueno H., and Yamamoto Y. Tetrahedron Lett. 44 (2003) 8935-8938
3. The reaction conditions were originally developed for the acetal cleavage giving enol ethers, see:. Miller R.D., and McKean D.R. Tetrahedron Lett. 23 (1982) 323-326
4. Also see:. Kadota I., Sakaihara T., and Yamamoto Y. Tetrahedron Lett. 37 (1996) 3195-3198
5. For the use of TMSI to cleave a benzyl ether, see:. Jung M.E., and Lyster M.A. J. Org. Chem. 42 (1977) 3761-3764
6. For an example of the deprotection of secondary MPM ethers using TMSI, see:. Gordon D.M., and Danishefsky S.J. J. Am. Chem. Soc. 114 (1992) 659-663
7. 3N has been reported, see:. Oriyama T., Yatabe K., Kawada Y., and Koga G. Synlett (1995) 45-46
8. The amounts of the reagents used were found to be enough to complete the reaction although the precise optimization was not performed. The use of large excess of the reagents did not affect the selectivity.
9. 3 was carried out for the conversion of the TMS ether, contained in the reaction mixture, into the primary alcohol.
10. 2NEt and piperidine are expected to be applicable.
11. The reaction was carried out with 1.2 equiv of TMSI, and quenched after 0.5 h. The use of an excess amount of TMSI would complete the reaction leading to 6. See Ref. 5.
12. 4 and concentrated. The residue was purified by column chromatography to give 5 (46 mg, 83%).