Mukaiyama-Suzuki Glycosylation

Mukaiyama-Suzuki Glycosylation

Overall Score4
  • Generality
  • Reagent Availability
  • Experimental User Friendliness
  • General Characteristics

The use of fluorinated sugars as glycosyl donors in glycosylation reactions was first reported by Mukaiyama. The original method employed a cationic tin-based Lewis acid as an activator, and later Suzuki reported more reactive and widely applicable systems employing cationic zirconocene and hafnocene complexes (the Suzuki modification).

Glycosyl fluorides can be activated by other reagents too, including LiClO4 and strong Brønsted acids like TfOH.

  • General References


  • Reaction Mechanism

Glycosyl fluorides are thermally and chemically more stable than other glycosyl halides thanks to the strong carbon-fluorine bond (C-F: 552 kJ/mol, C-Cl: 397 kJ/mol, C-Br: 280 kJ/mol). Glycosyl fluorides are stable enough to be purified by silica gel chromatography.

  • Examples

Total synthesis of benanomicin B.[1]


Total synthesis of gilvocarcin M[2]: Using phenol as an glycosyl acceptor, the O-glycoside rearranges to the C-glycoside at a high temperature.


  • Experimental Procedure

  • Experimental Tips

AgClO4 is very reactive but is potentially dangerous due to the risk of explosion. Trying AgOTf first is recommended.

  • References

  1. (a) Ohmori, K.; Tamiya, M.; Kitamura, M.; Kato, H.; Oorui, M.; Suzuki, K. Angew. Chem. Int. Ed. 2005, 44, 3871. DOI: 10.1002/anie.200501210 (b) Tamiya, M.; Ohmori, K.; Kitamura, M.; Kato, H.; Arai, T.; Oorui, M.; Suzuki, K. Chem. Eur. J. 2007, 13, 9791. DOI: 10.1002/chem.200700863
  2. (a) Matsumoto, T.; Hosoya, T.; Suzuki, K. J. Am. Chem. Soc. 1992, 114, 3568. DOI: 10.1021/ja00035a069 (b) Hosoya, T.; Takashiro, E.; Matsumoto, T.; Suzuki, K. J. Am. Chem. Soc. 1994, 116, 1004. DOI: 10.1021/ja00082a023
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