Fluorination

Living Edition
| Editors: Jinbo Hu, Teruo Umemoto

N,N-Dialkylaminosulfur Trifluoride Dethiofluorination

  • Mingyou Hu
  • Jinbo HuEmail author
Living reference work entry
DOI: https://doi.org/10.1007/978-981-10-1855-8_56-1
  • 2 Downloads

Introduction

N,N-Dialkylaminosulfur trifluorides are useful not only as deoxofluorination reagents but also as dethiofluorination reagents. Thus, the dialkylaminosulfur trifluorides reacted with organosulfur compounds such as thioesters, thioketones, etc. to give the corresponding dethiofluorinated compounds [1, 2]. On the other hand, a similar sulfur-mediated fluorination methodology was successfully applied to synthesize glycosyl fluorides, which were very useful synthetic intermediates in oligosaccharide chemistry [3, 4, 5, 6, 7, 8, 9].

Dethiofluorination of Thioesters, Thioketones, and Related Thio Compounds with DAST or Deoxofluor

In 1990, it was reported that thioesters reacted with N,N-diethylaminosulfur trifluorides (DAST) under mild conditions to give the corresponding difluoro ethers in high yields as shown in Eqs. ( 1) and ( 2) [ 1]. This is a useful method because esters themselves could not react with a dialkylaminosulfur trifluoride.
This is a preview of subscription content, log in to check access.

References

  1. 1.
    (a) Middleton, WJ (1975) New fluorinating Reagents. Dialkylaminosulfur fluorides. J Org Chem 40: 574–578. (b) Bunnelle WH, McKinnis BR, Narayanan BA (1990) Difluorination of esters. Preparation of α,α-difluoro ethers. J Org Chem 55:768–770.Google Scholar
  2. 2.
    Lal GS, Lobach E, Evans A (2000) Fluorination of thiocarbonyl compounds with bis(2-methoxyethyl)aminosulfur trifluoride (DeoxoFluor reagent): A facile synthesis of gem-difluorides. J Org Chem 65:4830–4832.CrossRefGoogle Scholar
  3. 3.
    Nicolaou KC, Delle RE, Papahatjis DP, Randall JL (1984) Practical synthesis of oligosaccharides. Partial synthesis of Avermectin Bla. J Am Chem Soc 106:4189–4192.CrossRefGoogle Scholar
  4. 4.
    Randall JL, Nicolaou KC (1988) Preparation and reactions of glycosyl fluorides. ACS Symposium Series Chapter 2, 374:13–28.Google Scholar
  5. 5.
    Yamashita S, Hayashi D, Nakano A, Hayashi Y, Hirama M (2016) Total synthesis of avermectin B1a revisited. J Antibiotics 69:31–50.CrossRefGoogle Scholar
  6. 6.
    Paterson I, Florence GJ, Heimann AC, Mackay AC (2005) Stereocontrolled total synthesis of (−)-Aurisides A and B. Angew Chem Int Ed 44:1130–1133.CrossRefGoogle Scholar
  7. 7.
    Hada N, Shimura R, Hakamata K, Kiyohara H, Yamada H, Takeda T, Kiuchi F (2015) Synthesis of model compounds related to linear β-D-(1→6)-galactosyl side-chains of polysaccharides from Astragalus mongholicus Bunge. Heterocycles 90:563–578.CrossRefGoogle Scholar
  8. 8.
    Nicolaou KC, Ladduwahetty T, Randall JL, Chucholowski A (1986) Stereospecific 1,2-migrations in carbohydrates. Stereocontrolled synthesis of α- and β-2-deoxyglycosides. J Am Chem Soc 108:2466–2467.CrossRefGoogle Scholar
  9. 9.
    Lin P-C, Adak AK, Ueng S-H, Huang L-D, Huang K-T, Ho JA, Lin C-C (2009) DAST-mediated regioselective anomeric group migration in saccharides. J Org Chem 74:4041–4048.CrossRefGoogle Scholar
  10. 10.
    Boswell GA, Jr, Ripka WC, Scribner RM, Tullock CW (1974) Fluorination by sulfur tetrafluoride. Org React 21:1–124.Google Scholar
  11. 11.
    Chang Y, Tewari A, Adi A-I, Bae C (2008) Direct nucleophilic fluorination of carbonyl groups of benzophenones and benzils with DeoxoFluor. Tetrahedron 64:9837–9842.CrossRefGoogle Scholar
  12. 12.
    Markovskij LN, Pashinnik VE, Kirsanov AV (1973) Application of dialkylaminosulfur trifluoride in the synthesis of fluoroorganic compounds. Synthesis 1973:787–789.CrossRefGoogle Scholar

Copyright information

© Springer Nature Singapore Pte Ltd. 2020

Authors and Affiliations

  1. 1.Department of Chemistry, School of Science, Xi’an Key Laboratory of Sustainable Energy Material Chemistry, and MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed MatterXi’an Jiaotong UniversityXi’anChina
  2. 2.Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular SynthesisShanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of SciencesShanghaiChina