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.
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.
Nicolaou
K C
KC
Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, La Jolla, California 92037, USA. kcn@scripps.edu
Fylaktakidou
K C
KC
Mitchell
H J
HJ
van Delft
F L
FL
Rodríguez
R M
RM
Conley
S R
SR
Jin
Z
Z
D000617:Aminoglycosides; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis* / Q000737:chemistry; D002241:Carbohydrates / Q000737:chemistry*; D004187:Disaccharides / Q000138:chemical synthesis*; D004952:Esters / Q000138:chemical synthesis; D006027:Glycosides / Q000138:chemical synthesis*; D015394:Molecular Structure; D012996:Solutions; D013057:Spectrum Analysis
D000617:Aminoglycosides; D000900:Anti-Bacterial Agents; D002241:Carbohydrates; D004187:Disaccharides; D004952:Esters; D006027:Glycosides; D012996:Solutions; C001202:evernimicin