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BF3 Fluorination for Preparing Alkyl Fluorides

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Fluorination

Part of the book series: Synthetic Organofluorine Chemistry ((SYOC))

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References

  1. Cresswell AJ; Davies SG, Roberts PM, Thomson JE (2015) Beyond the Balz−Schiemann Reaction: The Utility of Tetrafluoroborates and Boron Trifluoride as Nucleophilic Fluoride Sources. Chem Rev 115: 566−611.

    Article  CAS  Google Scholar 

  2. Jaber JJ, Mitsui K, Rychnovsky SD (2001) Stereoselectivity and regioselectivity in the segment-coupling Prins cyclization. J Org Chem 66: 4679–4686.

    Article  CAS  Google Scholar 

  3. Al-Mutairi EH, Crosby SR, Darzi J, Harding JR, Hughes RA, King CD, Simpson TJ, Smith RW, Willis CL (2001) Stereocontrolled synthesis of 2,4,5-trisubstituted tetrahydropyrans. Chem Commun 835-836.

    Google Scholar 

  4. Kataoka K, Ode Y, Matsumoto M, Nokami J (2006) Convenient synthesis of highly optically active 2,3,4,6-tetrasubstituted tetrahydropyrans via Prins cyclization reaction (PCR) of optically active homoallylic alcohols with aldehydes. Tetrahedron 62: 2471−2483.

    Article  CAS  Google Scholar 

  5. Launay GG, Slawin AMZ, O’Hagan D (2010) Prins fluorination cyclisations: preparation of 4-fluoro-pyran and -piperidine heterocycles. Beilstein J Org Chem 6: 41.

    Article  Google Scholar 

  6. Wölfling J, Frank É, Schneider G, Tietze LF (1998) Synthesis of azasteroids and D-homosteroids by intramolecular cyclization reactions of steroid arylimines. Synlett 1205−1206.

    Google Scholar 

  7. Wölfling J, Frank É, Schneider G, Tietze LF (1999) Synthesis of novel steroid alkaloids by cyclization of arylimines from estrone. Eur J Org Chem 3013–3020.

    Google Scholar 

  8. Berge J, Claridge S, Mann A, Muller C, Tyrrell E (1997) A diastereoselective synthesis of benzopyrans using a novel intramolecular Nicholas reaction in the key cyclisation step. Tetrahedron Lett 38: 685–686.

    Article  CAS  Google Scholar 

  9. Mann AL, Muller C, Tyrrell E (1998) A diastereoselective cobalt-mediated synthesis of benzopyrans using a novel variation of an intramolecular Nicholas reaction in the key cyclisation step: optimisation and biological evaluation. J Chem Soc Perkin Trans 1 1427–1438.

    Article  Google Scholar 

  10. Tyrrell E, Millet J, Tesfa KH, Williams N, Mann A, Tillett C, Muller C (2007) A study into asymmetric Nicholas cyclisation reactions. Tetrahedron 63: 12769−12778.

    Article  CAS  Google Scholar 

  11. Olier C, Gastaldi S, Christie SDR, Bertrand MP (2007) Unprecedented cyclization of Nicholas cations onto unactivated terminal alkenes: tandem trapping of cationic intermediates. Synlett 423−426.

    Google Scholar 

  12. Patel MM, Green JR (1999) [4+3] and fluorinative [4+3] cycloadditions of alkyne 1,4-diether dicobalt complexes. Chem Commun 509−510.

    Google Scholar 

  13. Lu Y, Green JR (2001) Tandem 4+3 cycloaddition/nucleophilic trapping reactions of butyne-1,4-diether dicobalt hexacarbonyl complexes. Synlett 243−247.

    Google Scholar 

  14. Cui J, Jia Q, Feng RZ, Liu SS, He T, Zhang C (2014) Boron trifluoride etherate functioning as a fluorine source in an iodosobenzene-mediated intramolecular aminofluorination of homoallylic amines. Org Lett 16: 1442−1445.

    Article  CAS  Google Scholar 

  15. Liu GQ, Li YM (2014) Regioselective (diacetoxyiodo)benzene-promoted halocyclization of unfunctionalized olefins. J Or. Chem 79: 10094−10109.

    Article  CAS  Google Scholar 

  16. Henbest HB, Wrigley TI (1957) Aspects of stereochemistry. Part IX. The formation of fluorohydrins from the cholesterol 5,6-epoxides and boron trifluoride–ether complex. J Chem Soc 4765−4768.

    Google Scholar 

  17. Bowers A, Ringold HJ (1963) Process for the production of 6-fluoro steroids. U.S. Patent 3115492.

    Google Scholar 

  18. Bowers A, CuÉllar Ibáñez L, Ringold HJ (1959) Steroids—CXX synthesis of halogenated steroid hormones: new routes to 6α-fluorotestosterone and the 6α- and 6β-fluoro analogs of progesterone. The synthesis of 6α- and 6β-fluoro reichstein’s compound “S” and 6α- and 6β-fluorodesoxycorticosterone acetate. Tetrahedron 7: 138−152.

    Article  CAS  Google Scholar 

  19. Fürst A, Plattner PA (1949) Über steroide und sexualhormone. 160. Mitteilung. 2α,3α- und 2β,3β-Oxido-chlolestane; konfiguration der 2-oxy-cholestane. Helv Chim Acta 32: 275−283.

    Article  Google Scholar 

  20. Blackett BN, Coxon JM, Hartshorn MP, Richards KE (1969) Reactions of epoxides—XXIV: the BF3-catalysed rearrangement of 4,5- and 5,6-epoxycholestanes. Tetrahedron 25: 4999−5005.

    Article  CAS  Google Scholar 

  21. Blunt JW, Hartshorn MP, Kirk DN (1965) Reactions of epoxides—V: rearrangements of 5,6-epoxy-6-methyl-cholestanes with boron trifluoride. Tetrahedron 21: 559−567.

    Article  CAS  Google Scholar 

  22. Guest IG, Marples BA (1970) Steroids. Part X. Boron trifluoride-catalysed rearrangements of 5,6-epoxy-3β-hydroxy- and 5,6-epoxy-3β-methoxy-steroids. J Chem Soc C 1626−1629.

    Google Scholar 

  23. St Enev V, Tsankova ET (1991) Lewis acid catalysed rearrangement of 7,11-epoxyisogermacrone. Formation of a new carbon skeleton. Tetrahedron 47: 6399−6406.

    Article  Google Scholar 

  24. Coxon JM, Hartshorn MP, Lewis AJ, Richards KE, Swallow WH (1969) Some rearrangements of substituted ethylene oxides. Tetrahedron 25: 4445−4448.

    Article  CAS  Google Scholar 

  25. Coxon JM, Hartshorn MP, Swallow WH (1974) Acetate participation in acyclic epoxide systems. acid-catalyzed rearrangements of trans- and cis-1-acetoxy-3,4-epoxypentanes, -4,5-epoxyhexanes, and -5,6-epoxyheptanes. J Org Chem 39: 1142−1148.

    Article  CAS  Google Scholar 

  26. Ashwell M, Jackson RFW, Kirk JM (1990) Preparation of α-substituted S-phenylthio esters from 2-nitro-2-phenylthio oxiranes. Tetrahedron 46: 7429−7442.

    Article  CAS  Google Scholar 

  27. House HO (1956) The rearrangement of α,β-epoxy ketones. III. The intramolecular nature of the rearrangement. J Am Chem Soc 78: 2298−2302.

    Article  CAS  Google Scholar 

  28. House HO, Ryerson GD (1961) The rearrangement of α,β-epoxy ketones. VIII. Effect of substituents on the rate of rearrangement J Am Chem Soc 83: 979−983.

    Article  CAS  Google Scholar 

  29. Weber FG, Giese H, Koeppel H, Reinhold M, Strobel R, Radeglia R, Storek W (1985) Substituenteneffekte in den 13C-NMR-spektren von diastereomeren chalkondihalogeniden. V. synthese, stereochemie und spektroskopie von chalkonfluorhydrinen. J Prakt Chem 327: 133−143.

    Article  CAS  Google Scholar 

  30. Cresswell AJ, Davies SG, Lee JA, Roberts PM, Russell AJ, Thomson JE, Tyte MJ (2010) β-Fluoroamphetamines via the stereoselective synthesis of benzylic fluorides. Org Lett 12: 2936−2939.

    Article  CAS  Google Scholar 

  31. Islas-González G, Puigjaner C, Vidal-Ferran A, Moyano A, Riera A, Pericàs MA (2004) Boron trifluoride-induced reactions of phenylglycidyl ethers: a convenient synthesis of enantiopure, stereodefined fluorohydrins. Tetrahedron Lett 45: 6337−6341.

    Article  Google Scholar 

  32. Giannini G (1996) The use of BF3·OEt2 in the synthesis of fluorinated anthracyclinones. Gazz Chim Ital 126: 771-772.

    CAS  Google Scholar 

  33. Lombardi P, Animati F, Cipollone A, Giannini G, Monteagudo E Arcamone F (1995) Synthesis and conformational preference of novel 8-fluoroanthracyclines. Acta Biochim Pol 42: 433−444.

    Article  CAS  Google Scholar 

  34. Voronkov MG, Fedotova LA (1967) Heteroatom derivatives of aziridine. IV. Reaction of ethylenimine with boron trifluoride. Chem Heterocycl Compd 2: 408−412.

    Article  Google Scholar 

  35. Sugihara Y, Iimura S, Nakayama J (2002) Aza-pinacol rearrangement: acid-catalyzed rearrangement of aziridines to imines. Chem Commun 134−135.

    Google Scholar 

  36. Legters J, Willems JGH, Thijs L, Zwanenburg B (1992) Synthesis of functionalized amino acids by ring-opening reactions of aliphatically substituted aziridine-2-carboxylic esters. Recl Trav Chim Pays-Bas 111: 59−68.

    Article  CAS  Google Scholar 

  37. Reddy R, Jaquith JB, Neelagiri VR, Saleh-Hanna S, Durst T (2002) Asymmetric synthesis of the highly methylated tryptophan portion of the hemiasterlin tripeptides. Org Lett 4: 695−697.

    Article  CAS  Google Scholar 

  38. Hu XE (2002) Lewis acid promoted regio- and stereoselective hetero nucleophilic addition to a piperidinyl aziridine. synthesis of trans 3-amino-4-substituted piperidines. Tetrahedron Lett 43: 5315−5318.

    Article  CAS  Google Scholar 

  39. Ding CH, Dai LX, Hou XL (2004) An efficient and highly regioselective fluorination of aziridines using BF3·OEt2 as fluorine source. Synlett: 2218−2220.

    Google Scholar 

  40. Pasceri R, Bartrum HE, Hayes CJ, Moody CJ (2012) Nucleophilic fluorination of β-ketoester derivatives with HBF4. Chem Commun 48: 12077−12079.

    Article  CAS  Google Scholar 

  41. Ohno M, Itoh M, Ohashi T, Eguchi S (1993) Ethyl 3-(1-adamantyl)-2-diazo-3-oxopropanoate: synthetic use for the preparation of some adamantane derivatives. Synthesis 793−796.

    Google Scholar 

  42. Heasley VL, Shellhamer DF, Gipe RK, Wiese HC, Oakes ML, Heasley GE (1980) Reaction of methyl hypochlorite with certain olefins in the presence of boron trifluoride. Tetrahedron Lett 21: 4133−4136.

    Article  CAS  Google Scholar 

  43. Heasley VL, Gipe RK, Martin JL, Wiese HC, Oakes ML, Shellhamer DF, Heasley GE, Robinson BL (1983) Boron trifluoride promoted reaction of alkyl hypohalites with alkenes. a new synthesis of fluoro halides. J Org Chem 48: 3195−3199.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China

    Chang-Hua Ding & Xue-Long Hou

Authors
  1. Chang-Hua Ding
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  2. Xue-Long Hou
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Correspondence to Chang-Hua Ding or Xue-Long Hou .

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Editors and Affiliations

  1. Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China

    Jinbo Hu

  2. R&D Center, Zhejiang Jiuzhou Pharmaceutical Co., Ltd, Taizhou, Zhejiang, China

    Teruo Umemoto

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Ding, CH., Hou, XL. (2018). BF3 Fluorination for Preparing Alkyl Fluorides. In: Hu, J., Umemoto, T. (eds) Fluorination. Synthetic Organofluorine Chemistry. Springer, Singapore. https://doi.org/10.1007/978-981-10-1855-8_43-1

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  • DOI: https://doi.org/10.1007/978-981-10-1855-8_43-1

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  • Print ISBN: 978-981-10-1855-8

  • Online ISBN: 978-981-10-1855-8

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