Total synthesis of everninomicin 13,384-1--Part 4: explorations of methodology; stereocontrolled synthesis of 1,1'-disaccharides, 1,2-seleno migrations in carbohydrates, and solution- and solid-phase synthesis of 2-deoxy glycosides and orthoesters

Chemistry. 2000 Sep 1;6(17):3166-85. doi: 10.1002/1521-3765(20000901)6:17<3166::aid-chem3166>;2-z.


Methods for the stereocontrolled construction of 1,1'-disaccharides, 2-deoxy glycosides, and orthoesters are reported. Specifically, a tin-acetal moiety was utilized to fix the anomeric stereochemistry of a carbohydrate acceptor leading to an efficient and stereoselective synthesis of 1,1'-disaccharides, while a newly discovered 1,2-phenylseleno migration reaction in carbohydrates opened entries to 2-deoxy glycosides and orthoesters. Thus, reaction of 2-hydroxy phenylselenoglycosides with DAST led to 2-phenylselenoglycosyl fluorides which reacted with carbohydrate acceptors to afford, stereoselectively, 2-phenylselenoglycosides. The latter compounds could be reductively deselenated to 2-deoxy glycosides or oxidatively converted to orthoesters via the corresponding ketene acetals.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Aminoglycosides*
  • Anti-Bacterial Agents / chemical synthesis*
  • Anti-Bacterial Agents / chemistry
  • Carbohydrates / chemistry*
  • Disaccharides / chemical synthesis*
  • Esters / chemical synthesis
  • Glycosides / chemical synthesis*
  • Molecular Structure
  • Solutions
  • Spectrum Analysis


  • Aminoglycosides
  • Anti-Bacterial Agents
  • Carbohydrates
  • Disaccharides
  • Esters
  • Glycosides
  • Solutions
  • evernimicin