Interplay of cascade oxidative cyclization and hydride shifts in the synthesis of the ABC spiroketal ring system of pectenotoxin-4.
Concepts: The formation of stereochemically defined bis-THF units through a double cyclization and a hydride-shift-initiated route to spiroketals is described (see scheme; Xc=chiral auxiliary). The resulting sequence has been used in a synthesis of the C1-16 fragment of the naturally occurring antitumor agent pectenotoxin-4.
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK. timothy.donohoe@chem.ox.ac.uk
Timothy J
TJ
Donohoe
Radosław M
RM
Lipiński
D003500:Cyclization; D005663:Furans / Q000138:chemical synthesis / Q000737:chemistry*; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013141:Spiro Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D000095702:Polyether Toxins
D005663:Furans; D018942:Macrolides; D013141:Spiro Compounds; C471226:pectenotoxin-4; D000095702:Polyether Toxins; C520774:spiroketal