Direct and convenient conversion of alcohols to fluorides

Organic Letters

Volumn 6, Issue 9, 2004, Pages 1465-1468

  Yin, Jingjun ^a   Zarkowsky, Devin S ^a   Thomas, David W ^a   Zhao, Matthew M ^a   Huffman, Mark A ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; FLUORIDE; FUNCTIONAL GROUP; REAGENT;

ARTICLE; CHEMICAL STRUCTURE; SYNTHESIS;

ACETONITRILES; ALCOHOLS; FLUORIDES; HYDROCARBONS, FLUORINATED; MOLECULAR STRUCTURE;

EID: 2442462243     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol049672a     Document Type: Article

References (55)

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22. DAST and analogues have compared favorably with most other fluorinating reagents. See ref 12.
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26. In those cases (ref 16), the fluorination could be realized via isolated triflate/imidazolylsulfonate.
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34. Formation of an imidazolylsulfonate 5b (also the precursor to 5c) would produce a chloride that would act as a nucleophile. Other sulfonates such as mesylate and tosylate are not active enough.
35. For a review of this commercially available reagent, see: McClinton, M. A. Aldrichimica Acta 1995, 28, 31.
36. Tetrabutylammonium fluoride (TBAF) is wet as a solid or solution. Metal fluorides such as KF and CsF need to be used in highly toxic solvents such as formamide and N-methylformamide and often give significant hydrolysis. See: (a) Fritz-Langhals, E. Tetrahedron: Asymmetry 1994, 5, 981. (b) Fritz-Langhals, E. Tetrahedron Lett. 1994, 35, 1851. (c) Ref 20b. Many modified metal fluoride reagents have been reported, but most are less efficient than TBAF: (d) Kim, D. W.; Song, C. E.; Chi, D. Y. J. Am. Chem. Soc. 2002, 124, 10278 and references therein.
37. Tetrabutylammonium fluoride (TBAF) is wet as a solid or solution. Metal fluorides such as KF and CsF need to be used in highly toxic solvents such as formamide and N-methylformamide and often give significant hydrolysis. See: (a) Fritz-Langhals, E. Tetrahedron: Asymmetry 1994, 5, 981. (b) Fritz-Langhals, E. Tetrahedron Lett. 1994, 35, 1851. (c) Ref 20b. Many modified metal fluoride reagents have been reported, but most are less efficient than TBAF: (d) Kim, D. W.; Song, C. E.; Chi, D. Y. J. Am. Chem. Soc. 2002, 124, 10278 and references therein.
38. Tetrabutylammonium fluoride (TBAF) is wet as a solid or solution. Metal fluorides such as KF and CsF need to be used in highly toxic solvents such as formamide and N-methylformamide and often give significant hydrolysis. See: (a) Fritz-Langhals, E. Tetrahedron: Asymmetry 1994, 5, 981. (b) Fritz-Langhals, E. Tetrahedron Lett. 1994, 35, 1851. (c) Ref 20b. Many modified metal fluoride reagents have been reported, but most are less efficient than TBAF: (d) Kim, D. W.; Song, C. E.; Chi, D. Y. J. Am. Chem. Soc. 2002, 124, 10278 and references therein.
39. Tetrabutylammonium fluoride (TBAF) is wet as a solid or solution. Metal fluorides such as KF and CsF need to be used in highly toxic solvents such as formamide and N-methylformamide and often give significant hydrolysis. See: (a) Fritz-Langhals, E. Tetrahedron: Asymmetry 1994, 5, 981. (b) Fritz-Langhals, E. Tetrahedron Lett. 1994, 35, 1851. (c) Ref 20b. Many modified metal fluoride reagents have been reported, but most are less efficient than TBAF: (d) Kim, D. W.; Song, C. E.; Chi, D. Y. J. Am. Chem. Soc. 2002, 124, 10278 and references therein.
40. (a) Giudicelli, M. B.; Picq, D.; Veyron, B. Tetrahedron Lett. 1990, 31, 6527.
41. (b) Ref 20a.
42. 3 might be formed as a gas.
43. One-pot conversion of few ethanols with a 2-electron-withdrawing group to fluorides using methane- or benzene-sulfonyl fluoride and KF in <60% yields has been reported: Pattison, F. L. M.; Millington, J. E. Can. J. Chem. 1956, 34, 757.
44. We only observed the sulfonate intermediate by LC or GC in very few cases.
45. 3) δ - 174.5.
46. LC yields are given due to the low boiling points and rather fast decomposition of the isolated products.
47. Treating 4 with the reagent combination failed to give 6.
48. LC-MS data and its water solubility support the proposed assignment. Reaction of primary triflate with pyridine to form water-soluble pyrdinium salt has been reported: Ambrose, M. G.; Binkley, R. W. J. Org. Chem. 1983, 48, 674. We also observed a similar product when pyridine was used.
49. Use of other bases such as pyridine, 2,6-lutidine, DABCO, DBU, TMEDA, and so on gave inferior results.
50. We generally saw slower and incomplete reactions for fluorination of primary alcohols using Deoxo-Fluor.
51. Deoxo-Fluor is known to react with aldehydes. See ref 13.
52. Johnson, A. L. J. Org. Chem. 1982, 47, 5220.
53. a of HF (3.2 in water).
54. 3 is also reported to be noncorrosive to glassware due to its almost neutral pH. See refs 20a and 22.
55. PBSF is immiscible with water. After stirring with water for 6 h at room temperature, it is still effective for fluorination, giving 12k (Table 3, entry 4).