Functional group transformation of α-trifluoromethylated alcohol derivatives

Tetrahedron Letters

Volumn 37, Issue 45, 1996, Pages 8187-8190

  Hagiwara, Toshiki ^a   Tanaka, Katsumi ^a   Fuchikami, Takamasa ^a  

^a SAGAMI CHEMICAL RESEARCH CENTER   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

NUCLEOSIDE DERIVATIVE; ORGANOFLUORINE DERIVATIVE;

ARTICLE; DRUG STRUCTURE; DRUG SYNTHESIS; FLUORINATION;

EID: 0030569311     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01857-6     Document Type: Article

References (21)

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3. (c) Welch, J. T. Tetrahedron, 1987, 43, 3123-3197.
4. (d) Mann, J. Chem. Soc. Rev. 1987, 16, 381-436.
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6. (f) Aoki, Y.; Nohira, H. Liq. Crystals 1995, 19, 15-19 and the references cited therein.
7. 2. (a) Surya Prakash, G. K. Nucleophilic Perfluoroalkylation of Organic Compounds Using Perfluoroalkyltrialkylsilanes. In Synthetic Fluorine Chemistry: Olah, G. A.; Chambers, R. D.; Surya Prakash, G. K. Eds.; John Wiley & Sons, Inc.: New York, 1992; Chapt. 10, pp. 227-245 and the references cited therein.
8. (b) Wang, Z.; Ruan, B. J. Fluorine Chem. 1994, 69, 1-3.
9. (c) Iseki, K.; Nagai, T.; Kobayashi, Y. Tetrahedron Lett. 1994, 35, 3137-3138.
10. 3. (a) Kitazume, T.; Ishikawa, N. J. Am. Chem. Soc. 1985, 107, 5186-5191.
11. (b) Tordeux, M.; Francese, C.; Wakselman, C. J. Chem. Soc. Parkin Trans. 1 1990, 1951-1957.
12. 4. Mitsunobu, O. Synthesis of Alcohols and Ethers. In Comprehensive Organic Synthesis: Trost, B. M.; Fleming, I. Eds.; Pergamon Press: Oxford, 1991; Vol. 6, Chapt. 1.1, pp. 18-22 and the references cited therein.
13. 7
14. 6. Vatcle, J.-M. Tetrahedron 1986, 42, 4443-4450.
15. 7. 2,2,2-Trifluoro-1-phenylethyl methanesulfonate (1) was prepared in 96% yield from 2,2,2-trifluoromethyl-1-phenylethanol and methanesulfonylchloride in the presence of triethylamine and 4-dimethylaminopyridine in ether. 1,1,1-Trifluoro-2-octyl methanesulfonate (2) was also prepared from 1,1,1-trifluoro-2-octanol in 69% yield.
16. 6 and shows that the introduction of oxygen nucleophiles is much difficult by the usual manners.
17. 9. Sato, T.; Otera, J. Synlett 1995, 336-338.
18. 3, 65 h, 84.2%, 19.5%; KF, 87 h, 79.6%, 51.3%. When CsF was used as a base, the hydrolysis of fluorinated mesylates was a severe side reaction because of the hygroscopicity of CsF, however, no hydrolysis of non-fluorinated mesylates took place at all under the similar reaction conditions. Therefore, a spray-dried KF is thought to be a most suitable base for the reaction of fluorinated mesylates in spite of its lower solubility.
19. 3): δ= -76.34 (d, J= 6.9 Hz).
20. 12. 1,1,1-Trifluoro-2-octyl trifluoromethanesulfonate (5) was prepared from 1,1,1-trifluoro-2-octanol and trifluoromethanesulfonic anhydride in the presence of triethylamine in 70% yield.
21. 13. Configurations of 4a and 4b were determined by comparing with (R)-4a prepared from (R)-1,1,1-trifluoro-2-octanol and benzoyl chloride. HPLC conditions: For 4a. Column: CHIRALPAK AD (DAISEL), Eluent: Hexane:2-Propanol = 400:1, Flow rate: 0.8 ml/min. For 4b. Column: CHIRALCEL OD (DAISEL), Eluent: Hexane:2-Propanol = 1000:1, Flow rate: 0.8 ml/min.