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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
Author(s) -
Nicolaou K. C.,
Fylaktakidou Konstantina C.,
Mitchell Helen J.,
van Delft Floris L.,
Rodríguez Rosa Maria,
Conley Scott R.,
Jin Zhendong
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20000901)6:17<3166::aid-chem3166>3.0.co;2-z
Subject(s) - chemistry , ketene , acetal , anomer , stereoselectivity , glycoside , carbohydrate , moiety , stereochemistry , combinatorial chemistry , carbohydrate synthesis , disaccharide , organic chemistry , catalysis
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.