Fused and spiro furanones from tetronic acid synthons: Oxa and azacycles featuring the butenolide ring

Diverse 4-O-allyl tetronates were obtained by reaction of allyl (alpha-hydroxy)carboxylates with keteneylidenetriphenylphosphorane (Ph3PCCO) in a domino reaction (addition – Wittig olefination) and by direct allylation of tetronic acid via Fischer esterification. 3-Allyl tetronic acids were generated by Claisen rearrangement of 4-O-allyl tetronates under microwave conditions; a subsequent Conia reaction produced the corresponding spiro cyclopropane furan-2,4-diones. Nucleophilic ring opening with diverse alcohols converted the spiro cyclopropane furan-2,4-diones to 3-beta-alkyloxypropyltetronic acids. When using O-benzyl isourea for the 4-O-alkylation of 3-allyl tetronic acids, the 3-benzyl derivatives were also formed (five examples were prepared). The Mitsunobu reaction proved to be a better way for the 4-O-alkylation of 3-allyl tetronic acids. 3,3-Diallyldihydrofuran-2,4-diones with two identical allyl residues were obtained by Tsuji-Trost-type Pd-catalysed allylation of either 4-O-allyltetronates or 3-allyltetronic acids. Pd assisted allylation of sodium 3-allyltetronate with a second allyl acetate gave mixed derivatives as did the Claisen rearrangement of 4-O-allyl 3-allyltetronates under microwave conditions. 3,3-Diallyldihydrofuran-2,4-diones were converted to butanolides with 3,3-spirocyclopentenyl or 3,4-cycloalkanyl annulation by ring closing methathesis with Grubbs’ catalysts. Natural product pesthetoxin was prepared via a double Ph3PCCO addition to alpha-hydroxy benzyl octanoate, thus demonstrating the utility of keteneylidenetriphenylphosphorane as a C2O building block. Finally, (-)-3-epi-blastmycinolactol was prepared enantioselectively via double hydrogenation of 3-but-2-enyl tetronic acid.

Level thesis:degree_level

thesis.doctoral

Grantor dc:publisher

Universität Bayreuth

Year

2006

Author dc:creator

• Urbina-Gonzalez, Juan-Manuel

Contributors dc:contributor

• Schobert, Rainer

Repository record source_url

https://epub.uni-bayreuth.de/id/eprint/771/

OAI identifier oai:identifier

oai:epub.uni-bayreuth.de:771